Polymerizable composition, process for producing cross linked polymers, and cross-linkable polymers

ABSTRACT

Composition comprising (a) catalytic amounts of a one-component catalyst for metathesis polymerization and (b) at least one polymer with strained cycloalkenylene radicals bonded in the polymer backbone, alone or as a mixture with strained cycloolefins. The composition can be polymerized thermally or photochemically by metathesis polymerization and is suitable for the production of shaped articles, coatings and relief images. The catalyst is selected from Ruthenium and Osmium compounds.

The present invention relates to a composition of unsaturated polymers, in the polymer backbone of which is bonded a strained cycloalkenylene, with a one-component catalyst for metathesis polymerization which is induced thermally or by actinic radiation; a process for the polymerization of the composition; materials coated with the composition or the polymerized composition, and shaped articles of the crosslinked polymers; and crosslinkable polymers.

Thermally induced ring-opening metathesis polymerization using catalytic amounts of metal catalysts has already been known for a relatively long time and described in many cases in the literature [see, for example, Ivin, K. J., Olefin Metathesis 1-12, Academic Press, London (1983)]. Polymers obtainable in this way are prepared industrially and are commercially obtainable, for example under the trade name Vestenamer®. The industrial preparation is carried out using highly reactive two-component catalysts, as a rule transition metal halides, for example WCl₆ and metal-alkylenes, for example zinc-, aluminium- or tin-alkylene. The polymerization or gelling starts immediately after a cycloolefin has been combined with the two catalyst components. The mixtures of cycloolefin and catalyst therefore have exceptionally short pot lives, and they are suitable in practice only in the reaction injection moulding process (RIM process). The severe heating of the reaction mixture due to the heat of reaction, which imposes very high technical requirements on a controlled reaction temperature, is also a disadvantage. It is therefore difficult to adhere to a polymer specification. WO 93/13171 describes air- and water-stable one-component and two-component catalysts based on molybdenum and tungsten compounds containing carbonyl groups and ruthenium and osmium compounds having at least one polyene ligand for thermal metathesis polymerization and a photoactivated metathesis polymerization of strained cycloolefins, in particular norbornene. No other polycyclic—above all non-fused polycyclic—cycloolefins are mentioned. The one-component catalysts of the ruthenium compounds used, that is to say [Ru(cumene)Cl₂]₂ and [(C₆H₆)Ru(CH₃CN)₂Cl]³⁰ PF₆ ⁻, can indeed be activated by UV irradiation; however, the storage stability of the compositions with norbornene are [sic] completely unsatisfactory. These catalysts can replace the known two-component catalysts only in adequately. Demonceau et al. [Demonceau, A., Noels, A. F., Saive, E., Hubert, A. J., J. Mol. Catal. 76: 123-132 (1992)] describe (p-cumene)RuCl₂P(C₆H₁₁)₃, (C₆H₅)₃]₃PRuCl₂ and (C₆H₅)_(3]) ₃PRuHCl as thermal catalysts for the ring-opening metathesis polymerization of norbornene, a fused polycycloolefin. Because their activity is too low, these catalysts have not found acceptance in industrial preparation. It is therefore proposed to increase the activity by the addition of diazoesters. It is also mentioned that only (p-cumene)RuCl₂P(C₆H₁₁)₃ is capable of polymerizing norbornene in a relatively short time at 60° C. Cyclooctene is also mentioned as a further monomer. No other cycloolefins are mentioned for the methatesis [sic] polymerization.

Petasis and Fu [Petasis, N. A., Fu, D., J. Am. Chem. Soc. 115: 7208-7214 (1993)] describe the thermal ring-opening metathesis polymerization of norbornene using bis-cyclopentadienyl-bis(trimethylsilyl)methyl-titanium(IV) as a thermally active catalyst. No other cycloolefins are mentioned for the metathesis polymerization.

No other more reactive one-component catalysts have yet been disclosed. It is furthermore also not known to use polymers with a strained cycloalkenylene in the polymer backbone for the preparation of crosslinked polymers.

It has now been found that polymers with strained cycloalkenylene radicals bonded in the polymer backbone are outstandingly suitable for the preparation of crosslinked polymers under the action particularly of one-component catalysts. The compositions are storage-stable and are even insensitive to air and oxygen, depending on the catalysts used, which allows processing without particular protective measures. Processing is easy and the processing possibilities are diverse, because no particular measures have to be taken owing to excessive reactivity. The polymers are suitable both for the production of solid shaped articles and for coatings with particularly high adhesive strength. The polymers can furthermore be used for the production of images by means of irradiation under a photomask and subsequent development of the non-exposed portions with a suitable solvent.

The invention first relates to a composition comprising (a) catalytic amounts of a one-component catalyst for metathesis polymerization and (b) at least one polymer with strained cycloalkenylene radicals bonded in the polymer backbone, alone or mixed with strained cycloolefins.

In a preferred embodiment, the polymers are those with recurring structural units of the formula (a) in the polymer backbone

in which

R₀₁ and R₀₂ independently of one another are H or C₁-C₆alkyl, or R₀₁ and R₀₂ together are a bond, and

A, together with the C—C group, forms an unsubstituted or substituted strained cycloolefin ring. The structural units of the formula (a) can be bonded directly or via bridge groups, preferably identical bridge groups.

Alkyl R₀₁ and R₀₂ preferably contain 1 to 4 C atoms; the alkyl is preferably methyl or ethyl. R₀₁ and R₀₂ are particularly preferably H.

The susbtituents for the cycloolefin ring can be, for example, C₁-C₈-, and preferably C₁-C₄alkyl or -alkoxy, for example methyl, ethyl, n- or i-propyl, n-, i- or t-butyl, methoxy, ethoxy or propyloxy; C₁-C₄haloalkyl or -alkoxy, for example trifluoromethyl, trichloromethyl, perfluoroethyl, bis(trifluoromethyl)methyl, trifluoromethoxy or bis(trifluoromethyl)methoxy; halogen, for example F, Cl or Br; —CN; —NH₂; secondary amino having 2 to 18 C atoms; tertiary amino having 3 to 18 C atoms; —C(O)—OR₀₃ or —C(O)—NR₀₃R₀₄, in which R₀₃ is H, C₁-C₁₈alkyl, phenyl or benzyl and R₀₄ independently has the meaning of R₀₃.

The strained cycloolefin ring can be monocyclic or polycyclic fused and/or bridged ring systems, for example with 2 to 6, preferably 2 to 4, and particularly preferably 2 or 3 rings, which are unsubstituted or substituted and can contain heteroatoms, for example O, S, N or Si, in one or more rings and/or fused aromatic or heteroaromatic rings, for example o-phenylene, o-naphthylene, o-pyridinylene or o-pyrimidinylene. The individual cyclic rings can contain 3 to 16, preferably 4 to 12, particularly preferably 5 to 8 ring members. The cyclic olefins can contain further non-aromatic double bonds, preferably 2 to 4 such additional double bonds, depending on the ring size.

Fused-on alicyclic rings preferably contain 3 to 8, particularly preferably 4 to 7, and especially preferably 5 or 6 ring C atoms. Fused-on aromatics are preferably naphthylene and, in particular, phenylene.

In a preferred embodiment, in formula (a)

R₀₁ and R₀₂ together are a bond, and A is unsubstituted or substituted C₁-C₁₂alkylene, preferably C₂-C₆alkylene; unsubstituted or substituted C₂-C₁₂heteroalkylene, preferably C₃-C₆heteroalkenyklene with at least one heteroatom from the group consisting of O, S and N; unsubstituted or substituted C₅-C₁₂cycloalkylene, preferably C₅-C₇cycloalkylene; unsubstituted or substituted C₄-C₁₂heterocycloalkylene, preferably C₄-C₇heterocycloalkylene with at least one heteroatom from the group consisting of O, S and N; unsubstituted or substituted C₂-C₁₂alkenylene, preferably C₂-C₆-alkenylene; unsubstituted or substituted C₃-C₁₂heteroalkenylene, preferably C₃-C₆heteroalkenylene with at least one heteroatom from the group consisting of O, S and N; unsubstituted or substituted C₅-C₁₂cycloalkenylene, preferably C₅-C₇cycloalkenylene; or unsubstituted or substituted C₄-C₁₂heterocycloalkenylene, preferably C₄-C₇heterocycloalkenylene with at least one heteroatom from the group consisting of O, S and N; or

R₀₁ and R₀₂ independently of one another are H or C₁-C₆alkyl and A is unsubstituted or substituted C₅-C₁₂-cycloalkenylene, preferably C₅-C₇cycloalkenylene; unsubstituted or substituted C₄-C₁₂heterocycloalkenylene, preferably C₄-C₇heterocycloalkenylene with at least one heteroatom from the group consisting of O, S and N; or unsubstituted or substituted C₅-C₁₂cycloalkdienylene, preferably C₅-C₇cycloalkdienylene; or

R₀₁ is a double bond together with a terminal C atom of the radical A; R₀₂ is H or C₁-C₆alkyl; and A is unsubstituted or substituted C₁-C₁₂alkylene, preferably C₂-C₆alkylene, unsubstituted or substituted C₃-C₁₂heteroalkylene, preferably C₃-C₆heteroalkylene with at least one heteroatom from the group consisting of O, S and N; unsubstituted or substituted C₅-C₁₂cycloalkylene, preferably C₅-C₇cycloalkylene; unsubstituted or substituted C₄-C₁₂heterocycloalkylene, preferably C₄-C₇heterocycloalkylene with at least one heteroatom from the group consisting of O, S and N; unsubstituted or substituted C₂-C₁₂alkenylene, preferably C₂-C₆alkenylene; unsubstituted or substituted C₃-C₁₂heteroalkenylene, preferably C₃-C₆heteroalkenylene with at least one heteroatom from the group consisting of O, S and N; unsubstituted or substituted C₅-C₁₂cycloalkenylene, preferably C₅-C₇cycloalkenylene; or unsubstituted or substituted C₄-C₁₂heterocycloalkenylene, preferably C₄-C₇heterocycloalkenylene with at least one heteroatom from the group consisting of O, S and N; or

R₀₁ and R₀₂ each are a double bond together with in each case a terminal C atom of the radical A, and A is unsubstituted or substituted C₃-C₁₂alkylene, preferably C₃-C₆alkylene; unsubstituted or substituted C₃-C₁₂heteroalkylene, preferably C₃-C₆heteroalkylene with at least one heteroatom from the group consisting of O, S and N; unsubstituted or substituted C₅-C₁₂cycloalkylene, preferably C₅-C₇cycloalkylene; or unsubstituted or substituted C₄-C₁₂heterocycloalkylene, preferably C₄-C₇heterocycloalkylene with at least one heteroatom from the group consisting of O, S and N;

it being possible for phenylene, C₄-C₈cycloalkylene or C₄-C₈heterocycloalkylene to be fused onto the alkylene, heteroalkylene, cycloalkylene, heterocycloalkylene, alkenylene, heteroalkenylene, cycloalkenylene, heterocycloalkenylene, alkdienylene, heteroalkdienylene, cycloalkdienylene and heterocycloalkdienylene.

It is known to the expert that cyclohexene can be polymerized by metathesis only with difficulty or not at all. Cyclohexene radicals of the formula (a) are therefore not preferred. Structural units of the formula (a) in which R₀₁ and R₀₂ together do not form a double bond are preferred.

Particularly preferably, in formula (a), R₀₁ and R₀₂ together are a bond, and A is unsubstituted or substituted C₂-C₆alkylene, unsubstituted or substituted C₃-C₇cycloalkylene, unsubstituted or substituted C₂-C₆alkenylene or unsubstituted or substituted C₅-C₇cycloalkenylene; or

R₀₁ and R₀₂ independently of one another are H or C₁-C₄alkyl and A is unsubstituted or substituted C₅-C₇cycloalkenylene; or

R₀₁ is a double bond together with a terminal C atom of the radical A; R₀₂ is H or C₁-C₄alkyl; and A is unsubstituted or substituted C₂-C₆alkenylene, unsubstituted or substituted C₅-C₇cycloalkylene, unsubstituted or substituted C₂-C₆alkenylene or unsubstituted or substituted C₅-C₇cycloalkenylene; or

R₀₁ and R₀₂ each are a double bond together with in each case a terminal C atom of the radical A and A is unsubstituted or substituted C₃-C₆alkylene or unsubstituted or substituted C₅-C₇-cycloalkylene.

The polymer backbone of the polymers to be used according to the invention can be built up in different ways. The polymers can be homo- or copolymers, containing structural elements of the formula (a) to the extent of at least 5 mol %, preferably 5 to 100 mol %, more preferably 5 to 80 mol %, even more preferably 10 to 70 mol %, particularly preferably 10 to 60 mol %, and especially preferably 20 to 50 mol %, based on the polymer. The polymers can be random copolymers or block copolymers.

The polymers used in the composition according to the invention include oligomers and polymers. The number of recurring structural units can accordingly be 2 to 10 000, preferably 5 to 5000, particularly preferably 10 to 1000, and especially preferably 20 to 500.

One group of polymers which are possible for the compositions according to the invention comprises, for example, the homo- and copolymers of linear polyepoxides, polyesters, polyamides, polyester-amides, polyurethanes and polyureas in which the divalent diepoxide, dicarboxylic acid or diisocyanate radicals, or in which the divalent diol or diamine radicals, or both of these radicals, contain strained cycloolefin radicals, and which, in the case of the copolymers of these divalent radicals, contain different diepoxide, dicarboxylic acid or diisocyanate, diol or diamine radicals. The strained cycloolefin ring preferably corresponds to the formula (a), including the preferred meanings.

The polyepoxides can be built up from diepoxides, as comonomers (α), having preferably 6 to 40, and particularly preferably 8 to 30 C atoms and diols, as comonomers (β), having preferably 2 to 200, more preferably 2 to 100, and particularly preferably 2 to 50 C atoms. Diepoxides with a strained cycloolefin ring contain preferably 6 to 40, and particularly preferably 10 to 30 C atoms. The diepoxides are preferably the diglycidyl ethers, which can easily be prepared. The monomeric diepoxides can be, for example, the diglycidyl ethers of aliphatic, cycloaliphatic, aromatic or araliphatic diols. Diols with a strained cycloolefin ring contain preferably 5 to 40, and particularly preferably 7 to 30 C atoms. The diols can be, for example, aliphatic, cycloaliphatic, aromatic or araliphatic diols. Diols and diepoxides are familiar to the expert and are not listed here. Among the diepoxides, the diglycidyl ethers and diglycidyl esters are preferred. Diepoxides and diols with a strained cycloolefin ring preferably contain a structural element of the formula (a), including the preferred meanings.

The polyepoxides can contain, for example, recurring structural elements chosen from the group of structural elements of the formulae (b), (c), (d) and (e)

[—CH₂—CH(OH)—CH₂—O—R₀₅—O—CH₂—CH(OH)—CH₂—O—  (b),

 —R₀₆—O—  (c),

[—CH₂—CH(OH)—CH₂—O—R₀₇—O—CH₂—CH(OH)—CH₂—O—  (d),

—R₀₈—O—  (e),

with the proviso that they contain at least structural elements of the formulae [sic] (b) or (c) or both, in which R₀₅ and R₀₆ independently of one another are a divalent radical of a strained cycloolefin or a divalent radical with a strained cycloolefin, R₀₇ is a divalent radical of a diglycidylether reduced by the glycidyloxy groups and R₀₈ is a divalent radical of a diol reduced by the hydroxyl group.

The polymer can contain in each case up to 100 mol % of the structural elements of the formulae (b) and (c) per mole of the polymer. If structural elements of the formulae (b) and (d) or (c) and (e) are present, advantageous mixing ratios are 5 to 95, preferably 10 to 80 mol % of structural elements of the formulae (b) and (c) and 95 to 5, preferably 90 to 20 mol % of the structural elements of the formulae (c) and (e), per mole of the polymer.

The polyepoxides are linear polyethers and are accessible in various ways, for example either by reaction of the diepoxides with the diols or by Diels-Alder reaction of polyepoxides with olefinically unsaturated diepoxide and/or diol structural units with open-chain or, preferably, cyclic 1,3-dienes to form strained cycloolefin rings.

R₀₅ and R₀₆ can be, for example, mono- or diolefinically unsaturated C₅-C₈cycloalkylene or fused polycyclic, preferably bi- or tricyclic, C₇-C₁₈cycloalkylene. Examples are cyclopentenylene, cycloheptenylene and cyclooctenylene. In a particularly preferred embodiment, R₀₅ and R₀₆ independently of one another are a norbornene radical of the formula (nr₁) or (nr₂)

R₀₇ and R₀₈ are preferably C₂-C₁₈-, preferably C₂-C₁₂alkylene, polyoxaalkylene having 2 to 50, preferably 2 to 10 oxalkylene units and 2 to 6, preferably 2 to 4 C atoms in the oxyalkylene, C₃-C₁₂-, preferably C₅-C₈cycloalkylene, C₅-C₈cycloalkylene-CH₂—, —CH₂—(C₅-C₈cycloalkylene)-CH₂—, C₆-C₁₄arylene, bisphenylene, benzylene, xylylene or —C₆H₄—X₀₁—C₆H₄—, where X₀₁ is O, S, SO, SO₂, CO, CO₂, NH, N(C₁-C₄-akyl), alkylidene having 1 to 18, preferably 1 to 12 C atoms or C₅-C₇cycloalkylidene. Some examples are ethylene, propylene, butylene, di-, tri- and tetraoxaethylene, cyclopentylene, cyclohexylene, cyclohexylene-CH₂—, —CH₂-cyclohexylene-CH₂—, phenylene, —C₆H₄—O—C₆H₄—, —C₆H₄—CH₂—C₆H₄—, —C₆H₄—CH(CH₃)—C₆H₄—, —C₆H₄—C(CH₃)₂—C₆H₄— and —C₆H₄—C₆H₁₀—C₆H₄—.

The polyepoxides are novel polymers and the invention likewise relates to these.

The polyesters can contain identical or different structural elements chosen from the group of structural elements of the formulae (f), (g), (h) and (i), where at least the structural elements of the formulae [sic] (f) or (g) or both must be present

—C(O)—R₀₉—C(O)—  (f),

—O—R₀₁₀—O—  (g),

—C(O)—R₀₁₁—C(O)—  (h),

—O—R₀₁₂—O—  (i),

in which R₀₉ and R₀₁₀ independently of one another are a divalent radical of a strained cycloolefin or a divalent radical with a strained cycloolefin, R₀₁₁ is a divalent radical of a dicarboxylic acid reduced by the carboxyl groups and R₀₁₂ is a divalent radical of a diol reduced by the hydroxyl group.

The polymer can contain in each case up to 100 mol % of the structural elements of the formulae (f) and (g), per mole of the polymer. If structural elements of the formulae (f) and (h) or (g) and (i) are present, advantageous mixing ratios are 5 to 95, preferably 10 to 80 mol % of structural elements of the formulae (f) and (h) and 95 to 5 preferably 90 to 20 mol % of the structural elements of the formulae (g) and (i).

The polyesters are preferably linear and accessible either by esterification or transesterification processes on the corresponding monomers, or by Diels-Alder reaction of polyesters with olefinically unsaturated dicarboxylic acid and/or diol structural units with open-chain or, preferably, cyclic 1,3-dienes to form strained cycloolefin rings. Mono-, di- or tricyclic dienes are preferably used for the Diels-Alder reaction.

R₀₉ and R₀₁₀ can be, for example, mono- or diolefinically unsaturated C₅-C₈cycloalkylene or fused polycyclic, preferably bi- or tricyclic C₇-C₁₈cycloalkylene. Examples are cyclopentenylene, cycloheptenylene, cyclooctenylene and, in particular, norbornene radicals of the formulae (nr₁) and (nr₂).

R₀₁₁, is preferably C₂-C₁₈-, preferably C₂-C₁₂alkylene or -alkenylene, C₃-C₁₂-, preferably C₅-C₈cycloalkylene or -cycloalkenylene, C₅-C₈cycloalkylene-CH₂—, —CH₂—(C₅-C₈cycloalkylene)-CH₂—, C₆-C₁₈arylene, bisphenylene, benzylene, xylylene or —C₆H₄—X₀₁—C₆H₄—, where X₀₁ is O, S, SO, S₂, CO, CO₂, NH, N(C₁-C₄alkyl), alkylidene having 1 to 18, preferably 1 to 12 C atoms, or C₅-C₇cycloalkylidene. Some examples are ethylene, propylene, butylene, hexylene, cyclopentylene, cyclohexylene, cyclohexylene-CH₂—, —CH₂-cyclohexylene-CH₂—, phenylene, naphthylene, —C₆H₄—CH₂—C₆H₄—, —C₆H₄—C₆H₄—, —C₆H₄—SO₂—C₆H₄—, —C₆H₄—CO—C₆H₄— and —C₆H₄—O—C₆H₄—. R₀₁₁ is preferably C₂-C₈alkylene, cyclohexylene or o-, m- or p-phenylene.

R₀₁₂ can preferably be C₂-C₁₈, preferably C₂-C₁₂alkylene, polyoxaalkylene having 2 to 50, preferably 2 to 10 oxaalkylene units and 2 to 6, preferably 2 to 4 C atoms in the oxyalkylene, C₃-C₁₂-, preferably C₅-C₈cycloalkylene, C₅-C₈-cycloalkylene-CH₂—, —CH₂—(C₅-C₈cycloalkylene)-CH₂—, C₆-C₁₄arylene, bisphenylene, benzylene, xylylene or —C₆H₄—X₀₁—C₆H₄—, where X₀₁ is O, S, SO, SO₂, CO, CO₂, NH, N(C₁-C₄alkyl), alkylidene having 1 to 18, preferably 1 to 12 C atoms, or C₅-C₇cycloalkylidene. Some examples are ethylene, propylene, butylene, hexylene, di-, tri- and tetreaoxaethylene, cyclopentylene, cyclohexylene, cyclohexylene-CH₂—, —CH₂-cyclohexylene-CH₂—, phenylene, —C₆H₄—CH₂—C₆H₄—, —C₆H₄—CH(CH₃)—C₆H₄—, —C₆H₄—C(CH₃)₂—C₆H₄—, —C₆H₄—C₆H₁₀—C₆H₄— and —C₆H₄—O—C₆H₄—. R₀₁₂ is particularly preferably C₂-C₆alkylene, which, in particular, is linear.

The polyesters are novel polymers and the invention likewise relates to these.

The polyamides can contain identical or different structural elements chosen from the group of structural elements of the formulae (j), (k), (l) and (m), where at least the structural elements of the formulae [sic] (j) or (k) or both must be present

—C(O)—R₀₁₃—C(O)—  (j),

—NH—R₀₁₄—NH—  (k),

—C(O)—R₀₁₅—C(O)—  (l),

—NH—R₀₁₆—NH—  (m),

in which R₀₁₃ and R₀₁₄ independently of one another are a divalent radical of a strained cycloolefin or a divalent radical with a strained cycloolefin, R₀₁₅ is a divalent radical of a dicarboxylic acid reduced by the carboxyl groups and R₀₁₆ is a divalent radical of a diamine reduced by the amino groups.

The polymer can contain in each case up to 100 mol % of the structural elements of the formulae (j) and (k) per mole of the polymer. If the structural elements of the formulae (j) and (l) or (k) and (m) are present, advantageous mixing ratios are 5 to 95, preferably 10 to 80 mol % of structural elements of the formulae (j) and (l) and 95 to 5, preferably 90 to 20 mol % of the structural elements of the formulae (k) and (m).

The polyamides are preferably linear and accessible either by or transamidation processes on the corresponding monomers, or by Diels-Alder reaction of polyamides with olefinically unsaturated dicarboxylic acid and/or diamine structural units with open-chain or preferably cyclic 1,3-dienes to form strained cycloolefin rings. Mono-, di- or tricyclic dienes are preferably used for the Diels-Alder reaction.

R₀₁₃ and R₀₁₄ can be, for example, mono- or diolefinically unsaturated C₅-C₈cycloalkylene or fused polycyclic, preferably bi- or tricyclic C₇-C₁₈cycloalkylene. Examples are cyclopentenylene, cycloheptenylene, cyclooctenylene and, in particular, norbornene radicals of the formulae (nr₁) and (nr₂).

R₀₁₅ is preferably C₂-C₁₈-, preferably C₂-C₁₂alkylene or -alkenylene, C₃-C₁₂-, preferably C₅-C₈cycloalkylene or -cycloalkenylene, C₅-C₈cycloalkylene-CH₂—, —CH₂—(C₅-C₈cycloalkylene)-CH₂—, C₆-C₁₈arylene, bisphenylene, benzylene, xylylene or —C₆H₄—X₀₁—C₆H₄—, where X₀₁ is O, S, SO, SO₂, CO, CO₂, NH, N(C₁-C₄alkyl) or alkylidene having 1 to 18, preferably 1 to 12 C atoms, or C₅-C₇cycloalkylidene. Some examples are ethylene, propylene, butylene, hexylene, cyclopentylene, cyclohexylene, cyclohexylene-CH₂—, —CH₂-cyclohexylene-CH₂—, phenylene, naphthylene, —C₆H₄—CH₂—C₆H₄—, —C₆H₄—C₆H₄—, —C₆H₄—SO₂—C₆H₄—, —C₆H₄—CO—C₆H₄— and —C₆H₄—O—C₆H₄—. R₀₁₅ is preferably C₂-C₈alkylene, cyclohexylene or o-, m- or p-phenylene.

R₀₁₆ can preferably be C₂-C₁₈-, preferably C₂-C₁₂alkylene, C₃-C₁₂-, preferably C₅-C₈cycloalkylene, C₅-C₈cycloalkylene-CH₂—, —CH₂—(C₅—C₈cycloalkylene)-CH₂—, C₆-C₁₄arylene, bisphenylene, benzylene, xylylene or —C₆H₄—X₀₁—C₆H₄—, where X₀₁ is O, S, SO, SO₂, CO, CO₂, NH, N(C₁-C₄alkyl) or alkylidene having 1 to 18, preferably 1 to 12 C atoms, or C₅-C₇cycloalkylidene. Some examples are ethylene, propylene, butylene, hexylene, di-, tri- and tetreaoxaethylene, cyclopentylene, cyclohexylene, cyclohexylene-CH₂—, —CH₂-cyclohexylene-CH₂—, phenylene, —C₆H₄—CH(CH₃)—C₆H₄—, C₆H₄—O—C₆H₄—, —C₆H₄—CH₂—C₆H₄—, —C₆H₄—C(CH₃)₂—C₆H₄— and —C₆H₄—C₆H₁₀—C₆H₄—. R₀₁₆ is particularly preferably C₂-C₆alkylene, which, in particular, is linear.

The polyamides can also contain structural units of 4 to 12-membered lactams, for example ε-caprolactam.

The polyamides are novel polymers and the invention likewise relates to these.

Polyester-amides are copolymers with diamines and diols which can contain, for example, the structural elements mentioned above for the polyesters and polyamides, in any combination.

The polyester-amides are novel polymers and the invention likewise relates to them.

The polyurethanes and polyureas can contain identical or different structural elements chosen from the group of structural elements of the formulae (n), (o), (p) and (q), where at least the structural elements of the formulae [sic] (n) or (o) or both must be present

—C(O)—NH—R₀₁₇—NH—C(O)—  (n),

—X₀₂—R₀₁₈—X₀₂—  (o),

—C(O)—NH—R₀₁₉—NH—C(O)—  (p),

—X₀₂—R₀₂₀—X₀₂—  (q),

in which R₀₁₇ and R₀₁₈ independently of one another are a divalent radical of a strained cycloolefin or a divalent radical with a strained cycloolefin, R₀₁₉ is a divalent radical of a diisocyanate reduced by the cyanate groups and R₀₂₀ is a divalent radical of a diamine or of a diol reduced by the amino or hydroxyl groups, and the X₀₂ independently of one another are —O— or —NH—.

The polyurethanes and -ureas are preferably linear and accessible either by addition polymerization of the corresponding monomers or by Diels-Alder reaction of polyurethanes or polyureas with olefinically unsaturated diisocyanate, diol- and/or diamine structural units with open-chain or preferably cyclic 1,3-dienes to form strained cycloolefin rings. Mono-, di- or tricyclic dienes are preferably used for the Diels-Alder reaction.

The polymer can contain in each case up to 100 mol % of the structural elements of the formulae (n) and (o) per mole of the polymer. If the structural elements of the formulae (n) and (o) or (p) and (q) are present, advantageous mixing ratios are 5 to 95, preferably 10 to 80 mol % of structural elements of the formulae (n) and (p) and 95 to 5, preferably 90 to 20 mol % of the structural elements of the formulae (o) and (q).

R₀₁₇ and R₀₁₈ can be, for example, mono- or diolefinically unsaturated C₅-C₈cycloalkylene or fused polycyclic, preferably bi- or tricyclic C₇-C₁₈cycloalkylene. Examples are cyclopentenylene, cycloheptenylene, cyclooctenylene and, in particular, norbornene radicals of the formulae (nr₁) and (nr₂).

R₀₁₉ is preferably C₂-C₁₈-, preferably C₂-C₁₂alkylene or -alkenylene, C₃-C₁₂-, preferably C₅-C₈cycloalkylene or -cycloalkenylene, C₅-C₈cycloalkylene-CH₂—, —CH₂—(C₅-C₈cycloalkylene)-CH₂—, C₆-C₁₈arylene, bisphenylene, benzylene, xylylene or —C₆H₄—X₀₁—C₆H₄—, where X₀₁ is O, S, SO, SO₂, CO, CO₂,NH, N(C₁-C₄alkyl) or alkylidene having 1 to 18, preferably 1 to 12 C atoms, or C₅-C₇cycloalkylidene. Some examples are ethylene, propylene, butylene, hexylene, cyclopentylene, cyclohexylene, isophoronylene, cyclohexylene-CH₂—, —CH₂-cyclohexylen-CH₂—, phenylene, naphthylene, toluylene, xylylene, —C₆H₄—C₆H₄—, —C₆H₄—CH₂—C₆H₄—, —C₆H₄—SO₂—C₆H₄—, —C₆H₄—CO—C₆H₄— and —C₆H₄—O—C₆H₄—.

R₀₂₀ can preferably be C₂-C₁₈-, preferably C₂-C₁₂alkylene, polyoxaalkylene having 2 to 50, preferably 2 to 10 oxaalkylene units and 2 to 6, preferably 2 to 4 C atoms in the oxyalkylene, C₃-C₁₂-, preferably C₅-C₈cycloalkylene, C₅-C₈cycloalkylene-CH₂—, —CH₂—(C₅-C₈cycloalkylene)-CH₂—, C₆-C₁₄arylene, bisphenylene, benzylene, xylylene, —C₆H₄—X₀₁—C₆H₄—, where X₀₁ is O, S, SO, SO₂, CO, CO₂, NH, N(C₁-C₄alkyl) or alkylidene having 1 to 18, preferably 1 to 12 C atoms, or C₅-C₇cycloalkylidene. Some examples are ethylene, propylene, butylene, hexylene, di-, tri- and tetreaoxaethylene, cyclopentylene, cyclohexylene, cyclohexylene-CH₂—, —CH₂-cyclohexylene-CH₂—, phenylene, —C₆H₄—CH₂—C₆H₄—, —C₆H₄—CH(CH₃)—C₆H₄—, —C₆H₄—C(CH₃)₂—C₆H₄—, —C₆H₄—C₆H₁₀—C₆H₄— and —C₆H₄—O—C₆H₄—. R₀₂₀ is particularly preferably C₂-C₆alkylene which, in particular, is linear.

The polyurethanes and polyureas are novel polymers and the invention likewise relates to these.

Polymers with a carbon backbone, of which various embodiments may be mentioned, are preferred according to the invention.

One embodiment can be essentially or completely linear metathesis polymers of fused at least bicyclic cycloaliphatic dienes which contain two olefinic double bonds in different rings. The individual rings can contain 3 to 12, preferably 5 to 8 ring C atoms. The polymers contain, for example, recurring structural elements of the formula (r)

═CH—R₀₂₁—CH═  (r),

in which R₀₂₁ is C₂-C₁₀-, preferably C₃-C₆alkylene, onto which a cycloalkenylene having a total of 5 to 8 C atoms is fused directly or via another fused-on cycloalkylene having 5 to 8 C atoms. Preferred examples are linear polynorbornadiene with recurring structural elements of the formula (r′)

or linear polydicyclopentadiene with recurring structural elements of the formula (r″)

or copolymers with these two recurring structural elements.

Polymers which are furthermore suitable are linear copolymers with a recurring structural element of the formula (r), preferably in each case one or both the above structural elements (r′) and (r″) and structural elements of the formula (r′″)

of a strained cycloolefin, in which

Q₃ is a linear or branched C₁-C₁₈alkylene which is unsubstituted or substituted by halogen, ═O, —CN, —NO₂, —COOM, —SO₃M, —PO₃M, —COO(M₁)_(1/2), —SO₃(M₁)_(1/2), —PO₃(M₁)_(1/2), C₁-C₂₀alkyl, R₁R₂R₃Si—(O)_(u)—, C₁-C₂₀hydroxyalkyl, C₁-C₂₀haloalkyl, C₁—C₆cyanoalkyl, C₃-C₈cycloalkyl,C₆-C₁₆aryl, C₇-C₁₆aralkyl, C₃-C₆heterocycloalkyl, C₃-C₁₆heteroaryl, C₄-C₁₆heteroarylalkyl or R₄—X—; or in which two adjacent C atoms are substituted by —CO—O—CO— or —CO—NR₅—CO—; or in which, possibly at adjacent carbon atoms, an alicyclic, aromatic or heteroaromatic ring is fused on which is unsubstituted or is substituted by halogen, —CN, —NO₂, R₆R₇R₈Si—(O)_(u)—, —COOM, —SO₃M, —PO₃M, —COO(M₁)_(1/2), —SO₃(M₁)_(1/2), —PO₃(M₁)_(1/2), C₁-C₂₀alkyl, C₁-C₂₀haloalkyl, C₁-C₂₀hydroxyalkyl, C₁-C₆cyanoalkyl, C₃-C₈cycloalkyl, C₆-C₁₆aryl, C₇-C₁₆aralkyl, C₃-C₆heterocycloalkyl, C₃-C₁₆heteroaryl, C₄-C₁₆heteroaralkyl or R₁₃—X₁—;

X and X₁ independently of one another are —O—, —S—, —CO—, —SO—, —SO₂—, —O—C(O)—, —C(O)—O—, —C(O)—NR₅—, —NR₁₀—C(O)—, —SO₂—O— or —O—SO₂—;

R₁, R₂ and R₃ independently of one another are C₁-C₁₂alkyl, C₁-C₁₂perfluoroalkyl, phenyl or benzyl;

R₄ and R₁₃ independently are C₁-C₂₀alkyl, C₁-C₂₀haloalkyl, C₁-C₂₀hydroxyalkyl, C₃-C₈cycloalkyl, C₆-C₁₆aryl, C₇-C₁₆aralkyl;

R₅ and R₁₀ independently of one another are hydrogen, C₁-C₁₂alkyl, phenyl or benzyl, the alkyl groups in turn being unsubstituted or substituted by C₁-C₁₂alkoxy or C₃-C₈cycloalkyl;

R₆, R₇ and R₈ independently of one another are C₁-C₁₂alkyl, C₁-C₁₂perfluoroalkyl, phenyl or benzyl;

M is an alkali metal and M₁ is an alkaline earth metal; and

u is 0 or 1;

the alicyclic ring formed with Q₃ possibly containing further non-aromatic double bonds;

Q₂ is hydrogen, C₁-C₂₀alkyl, C₁-C₂₀haloalkyl, C₁-C₁₂alkoxy, halogen, —CN, R₁₁—X₂—;

R₁₁ is C₁-C₂₀alkyl, C₁-C₂₀haloalkyl, C₁-C₂₀hydroxyalkyl, C₃-C₈cycloalkyl, C₆-C₁₆aryl or C₇-C₁₆aralkyl;

X₂ is —C(O)—O— or —C(O)—NR₁₂—;

R₁₂ is hydrogen, C₁-C₁₂alkyl, phenyl or benzyl;

the abovementioned cycloalkyl, heterocycloalkyl, aryl, heteroaryl, aralkyl and heteroaralkyl groups being unsubstituted or substituted by C₁-C₁₂alkyl, C₁-C₁₂alkoxy, —NO₂, —CN or halogen, and the heteroatoms of the abovementioned heterocycloalkyl, heteroaryl and heteroaralkyl groups being selected from the group —O—, —S—, —NR₉— and —N═; and

R₉ being hydrogen, C₁-C₁₂alkyl, phenyl or benzyl. Q₂ is with particular preference H.

In another embodiment, the polymers with a carbon backbone are copolymers of strained cycloolefins with fused at least bicyclic cycloaliphatic dienes which contain at least two olefinic double bonds in different rings, and ethylenically unsaturated comonomers. The individual rings can contain 3 to 12, preferably 5 to 8 ring C atoms. The polymers contain, for example, recurring structural elements of the formula (r) and of the formula (s)

═CH—R₀₂₁—CH═  (r),

in which

R₀₂₁ is C₂-C₁₀-, preferably C₂-C₄alkylene, onto which an alkenylene having 2 to 6, preferably 2 to 5 C atoms is bonded directly or via a fused-on cycloalkylene ring having 5 to 8 C atoms;

R₀₂₂ is H, F, C₁-C₁₂alkyl, —COOH, —C(O)O—C₁—C₁₂alkyl, —C(O)—NH—C₁-C₁₂alkyl or —C(O)—NH₂, preferably H, F, C₁-C₄alkyl, —COOH or —C(O)—C₁-C₆alkyl;

R₀₂₃ is H, F, Cl, CN or C₁-C₁₂alkyl, preferably H, F, Cl or C₁-C₄alkyl;

R₀₂₄ is H, F, Cl, CN, OH, C₁-C₁₂alkyl, C₁-C₁₂alkoxy, phenyl which is unsubstituted or substituted by OH, Cl, Br, C₁-C₄alkyl, C₁-C₄alkoxy, —C(O)OC₁-C₁₂alkyl, —C(O)—NH₂, —SO₃H, —COOH, C(O)—NH—C₁-C₁₂alkyl or —SO₃—C₁-C₁₂alkyl, or is —C(O)OH, —C(O)O—C₂-C₁₂hydroxyalkyl, —C(O)O—C₁-C₁₂alkyl, —C(O)—NH₂ or —C(O)—NH—C₁-C₁₂alkyl; and is preferably H, F, Cl, CN, OH, C₁-C₄alkyl, C₁-C₄alkoxy , pheny which is unsubstituted or substituted by OH, Cl, Br, C₁-C₄alkyl, C₁-C₄alkoxy, —COOH, —C(O)OC₁-C₁₄alkyl, —C(O)—NH₂, C(O)—NH—C₁-C₄alkyl, —SO₃H or —SO₃—C₁—C₄alkyl, or —COOH, —C(O)O—C₁-C₄alkyl, —C(O)O—C₂—C₆hydroxyalkyl, —C(O)—NH—C₁-C₄alkyl or —C(O)—NH₂; and

R₀₂₅ is H, F or C₁-C₁₂alkyl, preferably H or F.

Preferred examples of recurring structural elements of the formula (r) are structural elements of the formula (r′) and (r″).

The polymers can contain the structural elements of the formula (r) in an amount of 5 to 100, preferably 10 to 80, and particularly preferably 20 to 60 mol %, per mole of polymer.

The polymers, with the exception of the copolymers of norbornene and ethylene alone or together with other unsubstituted olefins, are novel and the invention likewise relates to these.

In another embodiment, the polymers with a carbon backbone are metathesis polymers of strained cycloolefins with a double bond in the ring, or copolymeric metathesis polymers of strained cycloolefins with a double bond in the ring and olefinically unsaturated comonomers, of which the olefinic double bonds in the polymer backbone are reacted partly or completely with open-chain or cyclic 1,3-dienes having 4 to 12, preferably 5 to 8 C atoms in a Diels-Alder reaction to give cycloalkenylene radicals having 6 to 14, preferably 7 to 12 C atoms. Preferably 5 to 80%, more preferably 5 to 60%, and in particular 10 to 50% of the double bonds are reacted.

In a preferred embodiment, these metathesis polymers contain recurring structural elements of the formula (t)

in which A₁ is mono- or bicyclic C₅-C₈cycloalkenylene.

The structural element of the formula (t) particularly preferably corresponds to norborn-1,2-enylene of the formula (nr₃)

In another preferred embodiment, the metathesis polymer contains recurring structural units of the formula (u)

and recurring structural elements of the formula (w)

—CH═CH—R₀₂₆—  (w),

in which A₁, together with the —CH—CH— group, is bicyclic C₅-C₈cycloalkenylene, preferably cyclopent-1,2-en-3,5-ylene, and R₀₂₆ is C₁-C₁₂-, preferably C₃-C₁₂alkylene, and, if desired, recurring structural elements of the formula (s).

The polymer can contain the structural elements of the formula (u) in an amount of 5 to 100, preferably 5 to 80, particularly preferably 5 to 60, and especially preferably 10 to 50 mol %, and the structural elements of the formula (w) in an amount of 95 to 0, preferably 95 to 20, particularly preferably 95 to 40 and especially preferably 90 to 50 mol %, per mole of polymer. They can contain the structural elements of the formula (s) in an amount of 0 to 80, preferably 0 to 60, and particularly preferably 0 to 50 mol %, per mole of a copolymer.

These metathesis polymers are novel and the invention likewise relates to them.

In another embodiment, the polymers with a carbon backbone are homo- and copolymers of 1,3-dienes and, if desired, olefinically unsaturated monomers, of which the olefinic double bonds in the polymer backbone are reacted partly or completely with open-chain or preferably cyclic 1,3-dienes having 4 to 12, preferably 5 to 8 C atoms in a Diels-Alder reaction to give cycloalkenylene radicals having 6 to 14, preferably 7 to 12 C atoms. Preferably 5 to 80%, more preferably 5 to 60%, and in particular 10 to 50% of the double bonds are reacted. Suitable 1,3-dienes are, for example, 1,3-butadiene, isoprene and chloroprene.

In a preferred embodiment, these polymers contain recurring structural elements of the formula (t).

The structural element of the formula (t) particularly preferably corresponds to norborn-1,2-enylene of the formula (nr₃).

In another preferred embodiment, the polymer contains recurring structural units of the formula (y)

and recurring structural elements of the formula (z)

—CH₂—CH═CR₀₂₇—CH₂—  (z),

in which A₁, together with the —CH—CR₀₂₇ group, is bicyclic C₅-C₈cycloalkenylene, preferably cyclopent-1,2-en-3,5-ylene, and R₀₂₇ is H, Cl or C₁-C₁₂-, preferably C₁-C₆alkyl, and, if desired, recurring structural elements of the formula (s).

The polymer can contain the structural elements of the formula (y) in an amount of 5 to 100, preferably 5 to 80, particularly preferably 5 to 60, and especially preferably 10 to 50 mol %, and the structural elements of the formula (z) in an amount of 95 to 0, preferably 95 to 20, particularly preferably 95 to 40, and especially preferably 90 to 50 mol %, per mole of polymer. It can contain the structural elements of the formula (s) in an amount of 0 to 80, preferably 0 to 60, and particularly preferably 0 to 50 mol %, per mole of a copolymer.

These polymers are novel and the invention likewise relates to them.

Polymers which are built up only from carbon and hydrogen are particularly preferred.

The processes for the preparation of the abovementioned polymers are known or analogous to known processes. The starting monomers and polymers are likewise known and are in some cases commercially obtainable or can be prepared by analogous processes. Diels-Alder reactions are advantageously carried out in solvents and expediently under increased pressure. Metathesis copolymers and processes for their preparation are described, for example, in U.S. Pat. No. 5,215,798. These polymers or metathesis polymers of strained cycloolefins can also be prepared with the catalysts described below. Diels-Alder reactions can be carried out analogously to the process described in EP 287 762.

The choice of the polymers to be used according to the invention depends chiefly on the intended use and the desired properties. The wide selection by modifications of the polymers allows tailor-made polymers to be provided for the most diverse uses. A further modification possibility results from the concomitant use of strained cycloolefins which are capable of metathesis polymerization, which means that, overall, adaptations specific to desired uses can be carried out.

A very large number of strained cycloolefins which the composition according to the invention can comprise as comonomers are known.

The cyclic olefins can be monocyclic or polycyclic fused and/or bridged ring systems, for example with two to four rings, which are unsubstituted or substituted and can contain heteroatoms, for example O, S, N or Si, in one or more rings and/or fused aromatic or heteroaromatic rings, for example o-phenylene, o-naphthylene, o-pyridinylene or o-pyrimidinylene. The individual cyclic rings can contain 3 to 16, preferably 3 to 12, and particularly preferably 3 to 8 ring members. The cyclic olefins can contain further non-aromatic double bonds, preferably 2 to 4 such additional double bonds, depending on the ring size. Ring substituents are those which are inert, that is to say do not impair the chemical stability and the heat stability of the catalysts. The cycloolefins are strained rings or ring systems.

If the cyclic olefins contain more than one double bond, for example 2 to 4 double bonds, crosslinked polymers can also be formed, depending on the reaction conditions, the monomer chosen and the amount of catalyst.

Fused-on alicyclic rings contain preferably 3 to 8, particularly preferably 4 to 7, and especially preferably 5 or 6 ring C atoms.

In a preferred embodiment, the comonomeric strained cycloolefins correspond to the formula I

in which

Q₁ is a radical having at least one carbon atom which, together with the —CH═CQ₂— group, forms an at least 3-membered alicyclic ring which may contain one or more heteroatoms chosen from the group consisting of silicon, phosporus, oxygen, nitrogen or sulfur; and which is unsubstituted or substituted by halogen, ═O, —CN, —NO₂, R₁R₂R₃Si—(O)_(u)—, —COOM, —SO₃M, —PO₃M, —COO(M₁)_(1/2), —SO₃(M₁)_(1/2), —PO₃(M₁)_(1/2), C₁-C₂₀alkyl, C₁-C₂₀hydroxyalkyl C₁-C₂₀haloalkyl, C₁-C₆cyanoalkyl, C₃-C₈cycloalkyl, C₆-C₁₆aryl, C₇-C₁₆aralkyl, C₃-C₆heterocycloalkyl, C₃-C₁₆heteroaryl, C₄-C₁₆heteroaralkyl or R₄—X—; or in which two adjacent C atoms are substituted by —CO—O—CO— or —CO—NR₅—CO—; or in which an alicyclic, aromatic or heteroaromatic ring which is unsubstituted or substituted by halogen, —CN, —NO₂, R₆R₇R₈Si—(O)_(u)—, —COOM, —SO₃M, —PO₃M, —COO(M₁)_(1/2), —SO₃(M₁)_(1/2), —PO₃(M₁)_(1/2), C₁-C₂₀alkyl, C₁-C₂₀haloalkyl, C₁-C₂₀hydroxyalkyl, C₁-C₆cyanoalkyl, C₃-C₈cycloalkyl, C₆-C16aryl, C₇-C₁₆aralkyl, C₃-C₆heterocycloalkyl, C₃-C₁₆heteroaryl, C₄-C₁₆heteroaralkyl or R₁₃—X₁— may be fused onto adjacent carbon atoms of the alicyclic ring;

X and X₁ independently of one another are —O—, —S—, —CO—, —SO—, —SO₂—, —O—C(O)—, —C(O)—O—, —C(O)—NR₅—, —NR₁₀—C(O)—, —SO₂—O— or —O—SO₂—;

R₁, R₂ and R₃ independently of one another are C₁-C₁₂alkyl, C₁-C₁₂perfluoroalkyl, phenyl or benzyl;

R₄ and R₁₃ independently are C₁-C₂₀alkyl, C₁-C₂₀haloalkyl, C₁-C₂₀hydroxyalkyl, C₃-C₈cycloalkyl, C₆-C₁₆aryl, C₇-C₁₆aralkyl;

R₅ and R₁₀ independently of one another are hydrogen, C₁-C₁₂alkyl, phenyl or benzyl, where the alkyl groups in their turn are unsubstituted or substituted by C₁-C₁₂alkoxy or C₃-C₈cycloalkyl;

R₆, R₇ and R₈ independently of one another are C₁-C₁₂alkyl, C₁-C₁₂perfluoroalkyl, phenyl or benzyl;

M is an alkali metal and M₁ is an alkaline earth metal; and

u is 0 or 1;

where the alicyclic ring formed with Q₁ may contain further non-aromatic double bonds;

Q₂ is hydrogen, C₁-C₂₀alkyl, C₁-C₂₀haloalkyl, C₁-C₁₂alkoxy, halogen, —CN, R₁₁—X₂—;

R₁₁ is C₁-C₂₀alkyl, C₁-C₂₀haloalkyl, C₁-C₂₀hydroxyalkyl, C₃-C₈cycloalkyl, C₆-C₁₆aryl or C₇-C16aralkyl;

X₂ is —C(O)—O— or —C(O)—NR₁₂—;

R₁₂ is hydrogen, C₁-C₁₂alkyl, phenyl or benzyl;

where the abovementioned cycloalkyl, heterocycloalkyl, aryl, heteroaryl, aralkyl and heteroaralkyl groups are unsubstituted or substituted by C₁-C₁₂alkyl, C₁C₁₂alkoxy, —NO₂, —CN or halogen and where the heteroatoms of the abovementioned heterocycloalkyl, heteroaryl and heteroaralkyl groups are chosen from the group consisting of —O—, —S—, —NR₉— and —N═; and R₉ is hydrogen, C₁-C₁₂alkyl, phenyl or benzyl.

Fused-on alicyclic rings preferably contain 3 to 8, particularly preferably 4 to 7, and especially preferably 5 or 6 ring C atoms.

If an asymmetric centre is present in the compounds of the formula I, this means that the compounds can occur in optically isomeric forms. Some compounds of the formula I can occur in tautomeric forms (for example keto-enol tautomerism). If an aliphatic C═C double bond is present, geometric isomerism (E form or Z form) can also occur. Exo-endo configurations are furthermore also possible. Formula I thus includes all the possible stereoisomers which are present in the form of enantiomers, tautomers, diastereomers, E/Z isomers or mixtures thereof.

In the definitions of the substituents, the alkyl, alkenyl and alkynyl groups can be straight-chain or branched. The same also applies to the alkyl or each alkyl part of alkoxy-, alkylthio-, alkoxycarbonyl- and of other alkyl-containing groups. These alkyl groups preferably contain 1 to 12, more preferably 1 to 8, and particularly preferably 1 to 4 C atoms. These alkenyl and alkynyl groups preferably contain 2 to 12, more preferably 2 to 8, and particularly preferably 2 to 4 C atoms.

Alkyl includes, for example, methyl, ethyl, isopropyl, n-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl and the various isomeric pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and eicosyl radicals.

Hydroxyalkyl includes, for example, hydroxymethyl, hydroxyethyl, 1-hydroxyisopropyl, 1-hydroxy-n-propyl, 2-hydroxy-n-butyl, 1-hydroxy-iso-butyl, 1-hydroxy-sec-butyl, 1-hydroxy-tert-butyl and the various isomeric pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and eicosyl radicals.

Haloalkyl includes, for example, fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, 2,2,2-trifluoroethyl, 2-fluoroethyl, 2-chloroethyl, 2,2,2-trichloroethyl and halogenated, in particular fluorinated or chlorinated, alkanes, for example the isopropyl, n-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, and the various isomeric pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and eicosyl radicals.

Alkenyl includes, for example, propenyl, isopropenyl, 2-butenyl, 3-butenyl, isobutenyl, n-penta-2,4-dienyl, 3-methyl-but-2-enyl, n-oct-2-enyl, n-dodec-2-enyl, iso-dodecenyl, n-octadec-2-enyl, n-octadec4-enyl.

Cycloalkyl is preferably C₅-C₈ cycloalkyl, in particular C₅- or C₆cycloalkyl. Some example are cyclopropyl, dimethylcyclopropyl, cyclobutyl, cyclopentyl, methylcyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl.

Cyanoalkyl includes, for example, cyanomethyl (methylnitrile [sic]), cyanoethyl (ethylnitrile [sic]), 1-cyanoisopropyl, 1-cyano-n-propyl, 2-cyano-n-butyl, 1-cyanoiso-butyl, 1-cyano-sec-butyl, 1-cyano-tert-butyl and various isomeric cyanopentyl and -hexyl radicals.

Aralkyl preferably contains 7 to 12 C atoms, and particularly preferably 7 to 10 C atoms. It can be, for example, benzyl, phenethyl, 3-phenylpropyl, α-methylbenzyl, phenbutyl or α,α-dimethylbenzyl.

Aryl preferably contains 6 to 10 C atoms. It can be, for example, phenyl, pentalene, indene, naphthalene, azulene or anthracene.

Heteroaryl preferably contains 4 or 5 C atoms and one or two heteroatoms from the group consisting of O, S and N. It can be, for example, pyrrole, furan, thiophene, oxazole, thiazole, pyridine, pyrazine, pyrimidine, pyridazine, indole, purin or quinoline.

Heterocycloalkyl preferably contains 4 or 5 C atoms and one or two heteroatoms from the group consisting of O, S and N. It can be, for example, oxirane, azirine, 1,2-oxathiolane, pyrazoline, pyrrolidine, piperidine, piperazine, morpholine, tetrahydrofuran or tetrahydrothiophene.

Alkoxy is, for example, methoxy, ethoxy, propyloxy, i-propyloxy, n-butyloxy, i-butyloxy, sec-butyloxy and t-butyloxy.

Alkali metal in the context of the present invention is to be understood as meaning lithium, sodium, potassium, rubidium and caesium, in particular lithium, sodium and potassium.

Alkaline earth metal in the context of the present invention is to be understood as meaning beryllium, magnesium, calcium, strontium and barium, in particular magnesium and calcium.

In the above definitions, halogen is to be understood as meaning fluorine, chlorine, bromine and iodine, preferably fluorine, chlorine and bromine.

Compounds of the formula I which are particularly suitable for the composition according to the invention are those in which Q₂ is hydrogen.

Compounds of the formula I which are furthermore preferred for the polymerization are those in which the alicyclic ring which Q₁ forms together with the —CH═CQ₂— group contains 3 to 16, more preferably 3 to 12, and particularly preferably 3 to 8 ring atoms, it being possible for this to be a monocyclic, bicyclic tricyclic or tetracyclic ring system.

The composition according to the invention particularly advantageously comprises compounds of the formula I in which

Q₁ is a radical having at least one carbon atom which, together with the —CH═CQ₂—group, forms a 3- to 20-membered alicyclic ring which may contain one or more heteroatoms chosen from the group consisting of silicon, oxygen, nitrogen and sulfur; and which is unsubstituted or substituted by halogen, ═O, —CN, —NO₂, R₁R₂R₃Si—(O)_(u)—, —COOM, —SO₃M, —PO₃M, —COO(M₁)_(1/2), —SO₃(M₁)_(1/2), —PO₃(M₁)₁₂, C₁-C₁₂alkyl, C₁-C₁₂haloalkyl, C₁-C₁₂hydroxyalkyl, C₁-C₄cyanoalkyl, C₃-C₆cycloalkyl, C₆-C₁₂aryl, C₇-C₁₂aralkyl, C₃-C₆heterocycloalkyl, C₃-C₁₂heteroaryl, C₄-C₁₂heteroaralkyl or R₄—X—; or in which two adjacent C atoms in this radical Q₁ are substituted by —CO—O—CO— or —CO—NR₅—CO—; or in which an alicyclic, aromatic or heteroaromatic ring which is unsubstituted or substituted by halogen, —CN, —NO₂, R₆R₇R₈Si—, —COOM, —SO₃M, —PO₃M, —COO(M₁)_(1/2), —SO₃(M₁)_(1/2), —PO₃(M₁)_(1/2), C₁-C₁₂alkyl, C₁-C₁₂haloalkyl, C₁-C₁₂hydroxyalkyl, C₁-C₄cyanoalkyl, C₃-C₆cycloalkyl, C₆-C₁₂aryl, C₇-C₁₂aralkyl, C₃-C₆heterocycloalkyl, C₃-C₁₂heteroaryl, C₄-C₁₂heteroaralkyl or R₁₃—X₁— may be fused onto adjacent carbon atoms;

X and X₁ independently of one another are —O—, —S—, —CO—, —SO—, —SO₂—, —O—C(O)—, —C(O)—O—, —C(O)—NR₅—, —NR₁₀—C(O)—, —SO₂—O— or —O—SO₂—;

R₁, R₂ and R₃ independently of one another are C₁-C₆alkyl, C₁-C₆perfluoroalkyl, phenyl or benzyl;

M is an alkali metal and M₁ is an alkaline earth metal;

R₄ and R₁₃ independently of one another are C₁-C₁₂alkyl, C₁-C₁₂haloalkyl, C₁-C₁₂hydroxyalkyl, C₃-C₈cycloalkyl, C₆-C₁₂aryl, C₇-C₁₂aralkyl;

R₅ and R₁₀ independently of one another are hydrogen, C₁-C₆alkyl, phenyl or benzyl, where the alkyl groups in their turn are unsubstituted or substituted by C₁-C₆alkoxy or C₃-C₆cycloalkyl;

R₆, R₇ and R₈ independently of one another are C₁-C₆alkyl, C₁-C₆perfluoroalkyl, phenyl or benzyl;

u is 0 or 1;

where the alicyclic ring formed with Q₁ may contain further non-aromatic double bonds;

Q₂ is hydrogen, C₁-C₁₂alkyl, C₁-C₁₂haloalkyl, C₁-C₆alkoxy, halogen, —CN, R₁₁—X₂—;

R₁₁ is C₁-C₁₂alkyl, C₁-C₁₂haloalkyl, C₁-C₁₂hydroxyalkyl, C₃-C₆cycloalkyl, C₆-C₁₂aryl or C₇-C₁₂aralkyl;

X₂ is —C(O)—O— or —C(O)—NR₁₂—; and

R₁₂ is hydrogen, C₁-C₆alkyl, phenyl or benzyl;

where the cycloalkyl, heterocycloalkyl, aryl, heteroaryl, aralkyl and heteroaralkyl groups are unsubstituted or substituted by C₁-C₆alkyl, C₁-C₆alkoxy, —NO₂, —CN or halogen, and where the heteroatoms of the heterocycloalkyl, heteroaryl and heteroaralkyl groups are chosen from the group consisting of —O—, —S—, —NR₉— and —N═; and

R₉ is hydrogen, C₁-C₆alkyl, phenyl or benzyl.

Compounds of the formula I from this group which are preferred are those in which

Q₁is a radical having at least one carbon atom which, together with the —CH═CQ₂— group, forms a 3- to 10-membered alicyclic ring which may contain a heteroatom chosen from the group consisting of silicon, oxygen, nitrogen and sulfur and is unsubstituted or substituted by halogen, —CN, —NO₂, R₁R₂R₃Si—, —COOM, —SO₃M, —PO₃M, —COO(M₁)_(1/2), —SO₃(M₁)_(1/2), —PO₃(M₁)_(1/2), C₁-C₆alkyl, C₁-C₆haloalkyl, C₁-C₆hydroxyalkyl, C₁-C₄cyanoalkyl, C₃-C₆cycloalkyl, phenyl, benzyl or R₄—X—; or in which an alicyclic, aromatic or heteroaromatic ring which is unsubstituted or substituted by halogen, —CN, —NO₂, R₆R₇R₈Si—, —COOM, —SO₃M, —PO₃M, —COO(M₁)_(1/2), —SO₃(M₁)_(1/2), —PO₃(M₁)_(1/2), C₁-C₆alkyl, C₁-C₆haloalkyl, C₁-C₆hydroxyalkyl, C₁-C₄cyanoalkyl, C₃-C₆cycloalkyl, phenyl, benzyl or R₁₃—X₁— may be fused onto adjacent carbon atoms;

R₁, R₂ and R₃ independently of one another are C₁-C₄alkyl, C₁-C₄perfluoroalkyl, phenyl or benzyl;

M is an alkali metal and M₁ is an alkaline earth metal;

R₄ and R₁₃ independently of one another are C₁-C₆alkyl, C₁-C₆haloalkyl, C₁-C₆hydroxyalkyl or C₃-C₆cycloalkyl;

X and X₁ independently of one another are —O—, —S—, —CO—, —SO— or —SO₂—;

R₆, R₇ and R₈ independently of one another are C₁-C₄alkyl, C₁-C₄perfluoroalkyl, phenyl or benzyl;

and Q₂ is hydrogen.

The composition according to the invention is particularly suitable for the polymerization of norbornene and norbornene derivatives. Of these norbornene derivatives, preferred derivatives are those which either correspond to the formula II

in which

X₃ is —CHR₁₆—, oxygen or sulfur;

R₁₄ and R₁₅ independently of one another are hydrogen, —CN, trifluoromethyl, (CH₃)₃Si—O—, (CH₃)₃Si— or —COOR₁₇; and

R₁₆ and R₁₇ independently of one another are hydrogen, C₁-C₁₂alkyl, phenyl or benzyl;

or correspond to the formula III

in which

X₄ is —CHR₁₉—, oxygen or sulfur;

R₁₉ is hydrogen, C₁-C₁₂alkyl, phenyl or benzyl; and

R₁₈ is hydrogen, C₁-C₆alkyl or halogen;

or correspond to the formula IV

in which

X₅ is CHR₂₂—, oxgen or sulfur;

R₂₂ is hydrogen, C₁-C₁₂alkyl, phenyl or benzyl;

R₂₀ and R₂₁ independently of one another are hydrogen, CN, trifluoromethyl, (CH₃)₃Si—O—, (CH₃)₃Si— or —COOR₂₃; and

R₂₃ is hydrogen, C₁-C₁₂alkyl, phenyl or benzyl;

or correspond to the formula V

in which

X₆ is —CHR₂₄—, oxygen or sulfur;

R₂₄ is hydrogen, C₁-C₁₂alkyl, phenyl or benzyl;

Y is oxygen or

 and

R₂₅ is hydrogen, methyl, ethyl or phenyl.

The following compounds of the formula I are particularly suitable, bi- and polycyclic systems being obtainable by Diels-Alder reactions:

The comonomeric polyfunctional strained cycloolefins can be compounds of the formula (f1)

(T)_(n)—U  (f1),

in which T is the radical of a strained cycloolefin, U is a direct bond or an n-valent bridge group and n is an integer from 2 to 8.

The cyclic olefins can be monocyclic or polycyclic fused and/or bridged ring systems, for example with two to four rings, which are unsubstituted or substituted and can contain heteroatoms, for example O, S, N or Si, in one or more rings and/or fused alicyclic, aromatic or heteroaromatic rings, for example o-cyclopentylene, o-phenylene, o-naphthylene, o-pyridinylene or o-pyimidinylene. The individual cyclic rings can contain 3 to 16, preferably 3 to 12, and particularly preferably 3 to 8 ring members. The cyclic olefins can contain further non-aromatic double bonds, preferably 2 to 4 such additional double bonds, depending on the ring size. The ring substituents are those which are inert, that is to say which do not impair the chemical stability of the one-component catalysts.

Fused-on alicyclic rings preferably contain 3 to 8, particularly preferably 4 to 7, and especially preferably 5 or 6 ring C atoms.

In a preferred embodiment, the radicals T in formula (f1) correspond to cycloolefin radicals of the formula (f2)

in which Q₁ and Q₂ have the abovementioned meanings, including the preferred meanings.

The position of the double bond in the ring of the formula (f2) with respect to the free bond essentially depends on the ring size and the preparation method for the compounds of the formula I.

The cycloalkenyl radical of the formula (f2) is particularly preferably unsubstituted or substituted by cyclopropenyl, cyclobutenyl, cyclopentenyl, cycloheptenyl, cyclooctenyl, cyclopentadienyl, cyclohexadienyl, cycloheptadienyl, cyclooctadienyl and norbornenyl or norbornenyl derivatives, for example 7-oxa-2,2,2-cycloheptene and the corresponding benzo derivatives. Substituents are preferably C₁-C₄alkyl and C₁-C₄alkoxy.

Particularly suitable radicals of the formula (f2) are norbornenyl and norbornenyl derivatives. Of these norbornenyl derivatives, particularly preferred derivatives are those which either correspond to the formula (f3)

in which

X₃ is —CHR₁₆—, oxygen or sulfur;

R₁₄ and R₁₅ independently of one another are hydrogen, —CN, trifluormethyl, (CH₃)₃Si—O—, (CH₃)₃Si— or —COOR₁₇; and

R₁₆ and R₁₇ independently of one another are hydrogen, C₁-C₁₂alkyl, phenyl or benzyl;

or correspond to the formula (f4)

in which

X₄ is —CHR₁₉—, oxygen or sulfur;

R₁₉ is hydrogen, C₁-C₁₂alkyl, phenyl or benzyl; and

R₁₈ is hydrogen, C₁-C₆alkyl or halogen.

The cycloalkenyl radical T in the formula (f1) is particularly preferably norbornenyl of the formula (nr₄)

In formula (f1), n is preferably an integer from 2 to 6, particularly preferably 2 to 4, and especially preferably 2 or 3.

In formula (t), U is preferably an n-valent bridge group.

Possible divalent bridge groups are, for example, those of the formula (f5)

—X₅—R₀₂₈—X₆—  (f5),

in which

X₅ and X₆ independently of one another are a direct bond, —O—, —CH₂—O—, —C(O)O—, —O(O)C—, —CH₂—O(O)C—, —C(O)—NR₀₂₉—, —R₀₂₉N—(O)C—, —NH—C(O)—NRC₀₂₉—, —O—C(O)—NH—, —CH₂—O—C(O)—NH— or —NH—C(O)—O—, and

R₀₂₈ is C₂-C₁₈alkylene, C₅-C₈cycloalkylene which is unsubstituted or substituted by C₁-C₄alkyl or C₁-C₄alkoxy, C₆-C₁₈arylene or C₇-C₁₉aralkylene which are unsubstituted or substituted by C₁-C₄alkyl or C₁-C₄alkoxy, or polyoxaalkylene having 2 to 12 oxaalkylene units and 2 to 6 C atoms in the alkylene, and

R₀₂₉ is H or C₁-C₆alkyl.

Alkylene R₀₂₈ preferably contains 2 to 12, and particularly preferably 2 to 8 C atoms. The alkylene can be linear or branched. Preferred cycloalkylene is cyclopentylene, and in particular cyclohexylene. Some examples of arylene are phenylene, naphthylene, biphenylene, biphenylene ether and anthracenylene. An example of aralkylene is benzylene. The polyoxaalkylene preferably contains 2 to 6, and particularly preferably 2 to 4 units, and preferably 2 or 3 C atoms in the alkylene.

In a preferred embodiment, in formula (f5),

a) X₅ and X₆ are a direct bond and R₀₂₈ is C₂-C₁₈alkylene, more preferably C₂-C₁₂alkylene, or

b) X₅ and X₆ are —O—, —CH₂—O—, —C(O)O—, —O(O)C—, —CH₂—O(O)C—, —CH₂—O—C(O)—NH—, —C(O)—NR₀₂₉— or —O—C(O)—NH— and R₀₂₈ is C₂-C₁₂alkylene, or phenylene, naphthylene or benzylene which are unsubstituted or substituted by C₁-C₄alkyl or C₁-C₄alkoxy, or —R₀₃₀—(O—R₀₃₀—)_(x)—OR₀₃₀—, in which x is a number from 2 to 4, and R₀₃₀ is —C₂-C₄alkylene.

Some examples of compounds of the formula (f5) with a divalent bridge group are

The compounds of the formula (f1) with a bridge group of the formula (f5) which is a pure hydrocarbon bridge are obtainable, for example, by means of a Diels-Alder reaction of a cyclic diene with a linear or branched aliphatic diene (see also EP 287 762), substance mixtures which are either further processed directly or separated beforehand by means of customary methods often being formed. Compounds of the formula (f1) with a bridge group of the formula (f5) in which X₅ and X₆ are not a direct bond are obtainable from the corresponding halides or dihalides, alcohols or diols, amines or diamines, carboxylic acids or dicarboxylic acids, or isocyanates or diisocyanates, via etherification, esterification or amidation reactions in a manner known per se.

Possible trivalent bridge groups are, for example, those of the formula (f6)

in which

X₅, X₆ and X₇ are —O—, —CH₂—O—, —C(O)O—, —O(O)C—, —CH₂—O(O)C—, —C(O)—NR₀₂₉—, —R₀₂₉N—(O)C—, —NH—C(O)—NR₀₂₉—, —O—C(O)—NH—, —CH₂—O—C(O)—NH— or —NH—C(O)—O—, and

R₀₃₁ is a trivalent aliphatic hydrocarbon radical having 3 to 20, preferably 3 to 12 C atoms, a trivalent cycloaliphatic radical which has 3 to 8, preferably 5 or 6 ring C atoms and is unsubstituted or substituted by C₁-C₄alkyl or C₁-C₄alkoxy, or a trivalent aromatic radical having 6 to 18, preferably 6 to 12 C atoms, which is unsubstituted or substituted by C₁-C₄alkyl or C₁-C₄alkoxy, a trivalent araliphatic radical having 7 to 19, preferably 7 to 12 C atoms, which is unsubstituted or substituted by C₁-C₄alkyl or C₁-C₄alkoxy, or a trivalent heteroaromatic radical having 3 to 13 C atoms and 1 to 3 heteroatoms from the group consisting of —O—, —N— and —S—, which is unsubstituted or substituted by C₁-C₄alkyl or C₁-C₄alkoxy, and

R₀₃₁ is H or C₁-C₆alkyl.

In a preferred embodiment, X₅, X₆ and X₇ are —O—, —CH₂—O—, —C(O)O—, —O(O)C—, —CH₂—O(O)C—, —C(O)—NR₀₂₉—, —O—C(O)—NH— or —CH₂—O—C(O)—NH—.

Preferred radicals R₀₃₁ are derived, for example, from triols, such as glycerol, trimethylolpropane, butanetriol, pentanetriol, hexanetriol, trihydroxycyclohexane, trihydroxybenzene and cyanuric acid; triamines, such as diethylenetriamine; tricarboxylic acids, such as cyclohexanetricarboxylic acid or trimellitic acid; and triisocyanates, such as benzene triisocyanate or cyanuric triisocyanate.

Some examples of compounds of the formula (f1) with a trivalent bridge group are

Possible tetravalent bridge groups are, for example, those of the formula (f7)

in which

X₅, X₆, X₇ and X₈ are —C(O)O—, —CH₂—O(O)C— or —C(O)—NR₀₂₉—, and

R₀₃₂ is a tetravalent aliphatic hydrocarbon radical having 4 to 20, preferably 4 to 12 C atoms, a tetravalent cycloaliphatic radical having 4 to 8, preferably 5 or 6 ring C atoms, which is unsubstituted or substituted by C₁-C₄alkyl or C₁-C₄alkoxy, or a tetravalent aromatic radical having 6 to 18, preferably 6 to 12 C atoms, which is unsubstituted or substituted by C₁-C₄alkyl or C₁-C₄alkoxy, a tetravalent araliphatic radical having 7 to 19, preferably 7 to 12 C atoms, which is unsubstituted or substituted by C₁-C₄alkyl or C₁-C₄alkoxy, or a tetravalent heteroaromatic radical having 3 to 13 C atoms and 1 to three heteroatoms from the group consisting of —O—, —N— and —S—, which is unsubstituted or substituted by C₁-C₄alkyl or C₁-C₄alkoxy, and

R₀₂₉ is H or C₁-C₆alkyl.

Some examples of tetrafunctional compounds from which R₀₃₂ can be derived are pentaerythritol, pyromellitic acid and 3,4,3′,4′-biphenyltetracarboxylic acid.

Preparation methods which can be used are the same methods as for the preparation of the abovementioned compounds with a di- or trivalent radical. Some examples of compounds of the formula (f1) with a tetravalent bridge group are

Polyols, such as dipentaerythritol or hexahydrohexane, which can be reacted with corresponding cycloolefinmonocarboxylic acids, may be mentioned as an example of compounds which are more than tetravalent and from which the bridge group can be derived.

Polymers and comonomers which contain only carbon and hydrogen are particularly preferred according to the invention. Norbornene is especially preferably contained as a comonomer in amounts of, for example, 20 to 60% by weight.

The comonomeric cycloolefins can be contained in an amount of 0.01 to 99% by weight, preferably 0.1 to 95% by weight, particularly preferably 1 to 90% by weight, and especially preferably 5 to 80% by weight, based on the polymers and monomers present in the composition.

The composition according to the invention can comprise solvents, especially if it is used for the production of coatings.

Suitable inert solvents are, for example, protic-polar and aprotic solvents, which can be used alone or in mixtures of at least two solvents. Examples are: ethers (dibutyl ether, tetrahydrofuran, dioxane, ethylene glycol monomethyl or dimethyl ether, ethylene glycol monoethyl or diethyl ether, diethylene glycol diethyl ether and triethylene glycol dimethyl ether), halogenated hydrocarbons (methylene chloride, chloroform, 1,2-dichlorethane, 1,1,1-trichlorethane and 1,1,2,2-tetrachlorethane), carboxylic acid esters and lactones (ethyl acetate, methyl propionate, ethyl benzoate, 2-methoxyethyl acetate, γ-butyrolactone, δ-valerolactone and pivalolactone), carboxylic acid amides and lactams (N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethylacetamide, tetramethylurea, hexamethylphosphoric acid triamide, γ-butyrolactam, ε-caprolactam, N-methylpyrrolidone, N-acetylpyrrolidone and N-methylcaprolactam), sulfoxides (dimethyl sulfoxide), sulfones (dimethyl sulfone, diethyl sulfone, trimethylene sulfone and tetramethylene sulfone), tertiary amines (N-methylpiperidine and N-methylmorpholine), aliphatic and aromatic hydrocarbons, for example petroleum ether, pentane, hexane, cyclohexane, methylcyclohexane, benzene or substituted benzenes (chlorobenzene, o-dichlorobenzene, 1,2,4-trichlorobenzene, nitrobenzene, toluene and xylene) and nitriles (acetonitrile, propionitrile, benzonitrile and phenylacetonitrile). Preferred solvents are aprotic polar and non-polar solvents.

The choice of solvents depends chiefly on the properties of the one-component catalysts, which must not be deactivated by the solvents used. Ruthenium and osmium catalysts can be used together with polar protic solvents, for example water or alkanols. These catalysts are also insensitive to air, oxygen and moisture, and corresponding crosslinkable compositions can be processed without particular protective measures. In the case of the other one-component catalysts, the exclusion of oxygen and moisture is advisable. The compositions are stable to storage, storage in the dark being advisable because of the sensitivity to light.

The composition according to the invention can comprise formulation auxiliaries and additions to improve the physical or mechanical properties. The compounds mentioned above as solvents are suitable as such substances. Known auxiliaries are stabilizers, for example antioxidants and light stabilizers, plasticizers, dyes, pigments, tixotropic [sic] agents, viscosity improvers, antistatics, lubricants and mould release auxiliaries.

The compositions according to the invention can be polymerized even if they also comprise fillers or reinforcing fillers in relatively large amounts. They can comprise these fillers in amounts of 0.1 to 90% by weight, preferably 0.5 to 80% by weight, more preferably 1 to 70% by weight, particularly preferably 5 to 60% by weight, and especially preferably 10 to 50% by weight, based on the monomers present.

Suitable reinforcing fillers are, in particular, those having a length to width ratio of at least 2. These are often fibrous or needle-shaped fillers. Some examples are fibres of plastics, carbon fibres, glass fibres, silicatic fibres, such as asbestos, whisker and wood fibres.

Suitable fillers are, for example, metal powders, wood flour, glass powders, glass beads, semimetal and metal oxides, for example SiO₂ (aerosils and quartz), corundum and titanium oxide, semimetal and metal nitrides, for example silicon nitride, boron nitride and aluminium nitride, semimetal and metal carbides [sic], metal carbonates (dolomite and CaCO₃), metal sulfates (barite and gypsum), rock powders and naturally occurring or synthetic minerals, chiefly from the silicate series, for example talc, wollastonite, bentonite and others.

Catalytic amounts for the one-component catalyst in the context of the present invention preferably means an amount of 0.001 to 20 mol %, more preferably 0.01 to 15 mol %, particularly preferably 0.01 to 10 mol %, and especially preferably 0.01 to 5 mol %, based on the amount of the monomer. Because of the high photocatalytic activity in ruthenium and osmium catalysts containing phosphene groups, amounts of 0.001 to 2% by weight are especially preferred in this case.

The compositions according to the invention advantageously comprise the novel thermal and/or photochemical one-component catalysts below:

1. Heat-stable ruthenium or osmium compounds which can be activated by radiation and have at least one photolabile ligand bonded to the ruthenium or osmium atom, the remaining coordination sites being satisfied by non-photolabile ligands.

Heat stability in the context of the invention means that the photocatalytically active metal compounds form no active species for the ring-opening metathesis polymerization when heated. For example, at room temperature to slightly elevated temperature, such as about +40° C., the catalyst can initiate no ring-opening metathesis polymerization with exclusion of light in the course of weeks. Only an insignificant amount (less than 0.2% by weight) of monomer is reacted during this period. The heat stability can be determined, for example, by storing a toluene solution with 20% by weight of monomer and 0.33% by weight of metal catalyst in the dark at 50° C. for 96 hours, and any amount of polymer formed, which can be detected by the build-up in viscosity and can be determined quantitatively by precipitation in a precipitant, for example ethanol, filtration and drying, is not more than 0.5% by weight, and preferably not more than 0.2% by weight.

Organic or inorganic compounds, atoms or ions which are coordinated onto a metal centre are designated as ligands for the ruthenium and osmium compounds to be used according to the invention.

Photolabile ligand in the context of the present invention means that when the catalyst is irradiated by light in the visible or ultraviolet spectral range, the ligand dissociates from the catalyst and forms a catalytically active species for the metathesis polymerization. Nonionic photolabile ligands are preferred according to the invention.

The photolabile ligands can be, for example, nitrogen (N₂), monocyclic, polycyclic or fused arenes having 6 to 24, preferably 6 to 18, and particularly preferably 6 to 12 C atoms, which are unsubstituted or substituted by OH, C₁-C₄alkyl, C₁-C₄alkoxy, C₆-C₁₂aryl or halogen, or monocyclic heteroarenes, fused heteroarenes or fused arene-heteroarenes having 3 to 22, preferably 4 to 16, and in particular 4 to 10 C atoms and 1 to 3 heteroatoms chosen from the group consisting of O, S and N, which are unsubstituted or substituted by C₁-C₄alkyl, C₁-C₄alkoxy or halogen; or aliphatic, cycloaliphatic, aromatic or araliphatic nitriles having 1 to 22, preferably 1 to 18, particularly preferably 1 to 12, and especially preferably 1 to 7 C atoms, which are unsubstituted or substituted by C₁-C₄alkyl, C₁-C₄alkoxy or halogen. The preferred substituents are methyl, ethyl, methoxy, ethoxy, fluorine, chlorine and bromine. The arenes and heteroarenes are preferably substituted by one or two radicals, and particularly preferably are unsubstituted. Among the heteroarenes, the electron-rich heteroarenes are preferred. The arenes and heteroarenes can be both π- and σ-bonded; in the last case, they are then the corresponding aryl and heteroaryl radicals. The aryl preferably contains 6 to 18, particularly preferably 6 to 12 C atoms. The heteroaryl preferably contains 4 to 16 C atoms.

Some examples of arenes and heteroarenes are benzene, p-cumene, biphenyl, naphthalene, anthracene, acenaphthene, fluorene, phenanthrene, pyrene, chrysene, fluoranthrene, furan, thiophene, pyrrole, pyridine, γ-pyran, γ-thiopyran, pyrimidine, pyrazine, indole, coumarone, thionaphthene, carbazole, dibenzofuran, dibenzothiophene, pyrazole, imidazole, benzimidazole, oxazole, thiazole, isoxazole, isothiazole, quinoline, isoquinoline, acridine, chromene, phenazine, phenoxazine, phenothiazine, triazines, thianthrene and purine. Preferred arenes and heteroarenes are benzene, naphthalene, thiophene and benzothiophene. The arene is especially preferably benzene and the heteroarene is especially preferably thiophene.

The nitriles can be substituted, for example by methoxy, ethoxy, fluorine or chlorine; the nitriles are preferably unsubstituted. The alkylnitriles are preferably linear. Some examples of nitriles are acetonitrile, propionitrile, butyronitrile, pentylnitrile, hexylnitrile, cyclopentyl- and cyclohexylnitrile, benzonitrile, methylbenzonitrile, benzylnitrile and naphthylnitrile. The nitriles are preferably linear C₁-C₄alkylnitriles or benzonitrile. Of the alkylnitriles, acetonitrile is particularly preferred.

In a preferred sub-group, the photolabile ligands are N₂, benzene which is unsubstituted or substituted by one to three C₁-C₄ alkyl, thiophene, benzonitrile or acetonitrile.

Non-photolabile ligand (also called highly coordinating ligand) in the context of the present invention means that when the catalyst is irradiated in the visible or near-ultraviolet spectral range, the ligand does not dissociate or dissociates to only an insignificant extent from the catalyst.

The non-photolabile ligands can be solvating inorganic and organic compounds which contain the heteroatoms O, S or N and are often also used as solvents, or cyclopentadienyl or indenyl which are unsubstituted or substituted by C₁-C₄alkyl, C₁-C₄alkoxy, (C₁-C₄alkyl)₃Si or (C₁-C₄alkyl)₃SiO—. Examples of such compounds are H₂O, H₂S and NH₃; halogenated or unhalogenated, in particular fluorinated or chlorinated, aliphatic or cycloaliphatic alcohols or mercaptans having 1 to 18, preferably 1 to 12, and particularly preferably 1 to 6 C atoms, aromatic alcohols or thiols having 6 to 18, preferably 6 to 12 C atoms, and araliphatic alcohols or thiols having 7 to 18, preferably 7 to 12 C atoms; aliphatic, cycloaliphatic, araliphatic or aromatic ethers, thioethers, sulfoxides, sulfones, ketones, aldehydes, carboxylic acid esters, lactones, optionally N—C₁-C₄mono- or -dialkylated carboxylic acid amides having 2 to 20, preferably 2 to 12, and in particular 2 to 6 C atoms and optionally N—C₁-C₄alkylated lactams; aliphatic, cycloaliphatic, araliphatic or aromatic, primary, secondary and tertiary amines having 1 to 20, preferably 1 to 12, and particularly preferably 1 to 6 C atoms; and unsubstituted or substituted cyclopentadienyls, for example cyclopentadienyl, indenyl and mono- or polymethylated or trimethylsilylated cyclopentadienyls or indenyls.

Examples of such non-photolabile ligands are methanol, ethanol, n- and i-propanol, n-, i- and t-butanol, 1,1,1-trifuoroethanol, bistrifluoromethylmethanol, tristrifluoromethylmethanol, pentanol, hexanol, methyl- or ethylmercaptan, cyclopentanol, cyclohexanol, cyclohexylmercaptan, phenol, methyophenol, fluorophenol, phenylmercaptan, benzydmercaptan, benzyl alcohol, diethyl ether, dimethyl ether, diisopropyl ether, di-n- or di-t-butyl ether, tetrahydrofuran, tetrahydropyran, dioxane, diethyl thioether, tetrahydrothiophene, dimethyl sulfoxide, diethyl sulfoxide, tetra- and pentamethylene sulfoxide, dimethyl sulfone, diethyl sulfone, tetra- and pentamethylene sulfone, acetone, methyl ethyl ketone, diethyl ketone, phenyl methyl ketone, methyl isobutyl ketone, benzyl methyl ketone, acetaldehyde, propionaldehyde, trifluoroacetaldehyde, benzaldehyde, ethyl acetate, butyrolactone, dimethylformamide, dimethylacetamide, pyrrolidone and N-methylpyrrolidone, indenyl, cyclopentadienyl, methyl- or dimethyl- or pentamethylcyclopentadienyl and trimethylsilylcyclopentadienyl.

The primary amines can be those of the formula R₂₅NH₂, the secondary amines those of the formula R₂₅R₂₆NH and the tertiary amines those of the formula R₂₅R₂₆R₂₇N, in which R₂₅ is C₁-C₁₈alkyl, C₅- or C₆cycloalkyl which is unsubstituted or substituted by C₁-C₄alkyl or C₁-C₄alkoxy, or C₆-C₁₈aryl or C₇-C₁₂aralkyl which are unsubstituted or substituted by C₁-C₄alkyl or C₁-C₄alkoxy, R₂₆ independently has the meaning of R₂₅, or R₂₅ and R₂₆ together are tetramethylene, pentamethylene, 3-oxa-1,5-pentylene or —CH₂—CH₂—NH—CH₂—CH₂— or —CH₂—CH₂—N(C₁-C₄alkyl)—CH₂—CH₂—, R₂₅ and R₂₆ independently of one another have the abovementioned meanings, and R₂₇ independently has the meaning of R₂₅. The alkyl preferably contains 1 to 12, and particularly preferably 1 to 6 C atoms. The aryl preferably contains 6 to 12 C atoms and the aralkyl preferably contains 7 to 9 C atoms. Examples of amines are methyl-, dimethyl-, trimethyl-, ethyl-, diethyl-, triethyl-, methylethyl-, dimethylethyl, n-propyl-, di-n-propyl-, tri-n-butyl-, cyclo-hexyl-, phenyl- and benzylamine, and pyrrolidone, N-methylpyrrolidine, piperidine, piperazine, morpholine and N-methylmorpholine.

In a preferred sub-group, the non-photolabile ligands are H₂O, NH₃ and unsubstituted or partly or completely fluorinated C₁-C₄alkanols. H₂O, NH₃, cyclopentadienyl, methanol and ethanol are especially preferred.

The ruthenium and osmium compounds to be used according to the invention can be mono- or polynuclear, for example those having two or three metal centres. The metal atoms can be bonded here via a bridge group or metal-metal bonds.

Among the compounds with a plurallity of metal centres, those of the formula VIIIa or VIIIb

in which Lig is a photolabile ligand and Me is Ru or Os, A₉, A₁₀ and A₁₁ are a divalent bridge group, and Y is a monovalent non-coordinating anion, are preferred. The bridge group is preferably ionic, and particularly preferably a halide, especially preferably chloride, bromide or iodide. The photolabile ligand is preferably identical or different arenes, and Y can be the anions listed below, and especially chloride, bromide or iodide. An example of such complexes is [C₆H₆Ru(Cl)₃RuC₆H₆]Cl. Preferred catalysts according to the invention correspond to the formula IX

[(Me^(+n))(L₁ ²¹)_(m)(L₂ ^(z2))_(o)(L₃ ^(z3))_(p)(L₄ ^(z4))_(q)(L₅ ^(z5))_(r)(L₆ ^(z6))_(s)](L₇ ^(z7))_(t)  (IX)

in which

Me is ruthenium or osmium;

n is 0, 1, 2, 3, 4, 5, 6, 7 or 8;

L₁ is a photolabile ligand;

L₂, L₃, L₄, L₅ and L₆ independently of one another are a non-photolabile or a photolabile ligand;

m is 1, 2, 3, 4, 5 or 6;

o, p, q, r and s independently of one another are 0, 1, 2, 3, 4 or 5;

z₁, z₂, z₃, z₄, z₅, z₆ and z₇ independently of one another are −4, −3, −2, −1, 0, +1 or +2; and

L₇ is a non-coordinating cation or anion;

where the sum of m+o+p+q+r+s is an integer from 2 to 6 and t is the quotient of (n+m·z₁+o·z₂+p·z₃+q·z₄+r·z₅+s·z₆)/z₇.

In the formula IX, L₇ is preferably halogen (for example Cl, Br and I), the anion of an oxygen acid BF₄, PF₆, SiF₆ or AsF₆.

The anions of oxygen acids can be, for example, sulfate, phosphate, perchlorate, perbromate, periodate, antimonate, arsenate, nitrate, carbonate, the anion of a C₁-C₈carboxylic acid, for example formate, acetate, propionate, butyrate, benzoate, phenylacetate or mono-, di- or trichloro- or -fluoroacetate, sulfonates, for example methylsulfonate, ethylsulfonate, propylsulfonate, butylsulfonate, trifluoromethylsulfonate (triflate) or phenylsulfonate or benzylsulfonate which are unsubstituted or substituted by C₁-C₄alkyl, C₁-C₄alkoxy or halogen, in particular fluorine, chlorine or bromine, for example tosylate, mesylate, brosylate, p-methoxy- or p-ethoxyphenylsulfonate, pentafluorophenylsulfonate or 2,4,6-triisopropylsulfonate, and phosphonates, for example methylphosphonate, ethylphosphonate, propylphosphonate, butylphosphonate, phenylphosphonate, p-methylphenylphosphanate and benzylphosphonate.

Preferably, in the formula IX, Me is ruthenium, in particular Ru²⁺.

A group of compounds of the formula IX which is to be singled out in particular is that in which the ligands L₁, L₂, L₃, L₄, L₅ and L₆ independently of one another are aliphatic, cycloaliphatic, aromatic or araliphatic nitriles having 1 to 22 C atoms, which are unsubstituted or substituted by C₁-C₄alkyl, C₁-C₄alkoxy or halogen, or C₆-C₁₈aryl; or L₁, L₂ and L₃ together are monocyclic, polycyclic or fused arenes having 6 to 24, preferably 6 to 18, and particularly preferably 6 to 12 C atoms, which are unsubstituted or substitututed by —OH, C₁-C₄alkyl, C₁-C₄alkoxy, C₆-C₁₂aryl or halogen, or monocyclic heteroarenes, fused heteroarenes or fused arene-heteroarenes having 4 to 22 C atoms and 1 to 3 heteroatoms chosen from the group consisting of O, S, and N, which are unsubstituted or substituted by —OH, C₁-C₄alkyl, C₁-C₄alkoxy or halogen, and L₄, L₅ and L₆ together have the same meaning, or individually, independently of one another, are N₂ or the said nitrile or the said C₆-C₁₈aryl.

A preferred sub-group of the above compounds of the formula IX are those in which the ligands L₁, L₂, L₃, L₄, L₅ and L₆ independently of one another are N₂, C₁-C₂₀alkylnitrile, C₆-C₁₂arylnitrile, C₇-C₁₂aralkylnitrile, C₆-C₁₂aryl or L₁, L₂ and L₃ each together are the groups A₁ or A₂

in which

R₂₈, R₂₉, R₃₀, R₃₁, R₃₂, R₃₃, R₃₄, R₃₅, R₃₆ and R₃₇ independently of one another are hydrogen, C₁-C₂₀alkyl, C₁-C₂₀alkoxy, aryl or SiR₃₈R₃₉R₄₀ where, in the case of groups A₁ and A₂ on adjacent carbon atoms, an aromatic or heteroaromatic ring, the heteroatoms of which are chosen from oxygen, sulfur and nitrogen, can be fused on; and R₃₈, R₃₉ and R₄₀ independently of one another are C₁-C₁₂alkyl, C₅- or C₆cycloalkyl, or phenyl or benzyl which are unsubstituted or substituted by C₁-C₆alkyl or C₁-C₆alkoxy, preferably C₁-C₈alkyl, phenyl or benzyl, particularly preferably C₁-C₄alkyl, phenyl or benzyl, and L₄, L₅ and L₆ likewise together have this meaning or are each individually N₂, the said nitriles or the said C₆-C₁₂aryl, or are an arene or heteroarene.

From this group of compounds of the formula IX which is to be singled out, preferred compounds are those in which L₁, L₂, L₃, L₄, L₅ and L₆ independently of one another are C₁-C₁₂alkylnitrile, C₆-C₁₂arylnitrile, or L₁, L₂ and L₃ each together are the groups A₁ or A₂ and L₄, L₅ and L₆ likewise together have this meaning or each individually are N₂, the said nitriles or the said arene or heteroarene of the formulae A₁ and A₂, in which R₂₈, R₂₉, R₃₀, R₃₁, R₃₂, R₃₃, R₃₄, R₃₅, R₃₆ and R₃₇ independently of one another are hydrogen, C₁-C₆alkyl, C₁-C₆alkoxy, SiR₃₈R₃₉R₄₀ or phenyl, where, in the case of the groups A₁ and A₂ on adjacent carbon atoms, a benzene ring can be fused on, and R₃₈, R₃₉ and R₄₀ are methyl, ethyl or phenyl.

In an especially preferred embodiment of the process according to the invention, the catalyst used is that of the formula IX, in which L₁, L₂, L₃, L₄, L₅ and L₆ independently of one another are methylnitrile, ethylnitrile or phenylnitrile, or L₁, L₂ and L₃ each together are the groups A₁ or A₂ and L₄, L₅, and L₆ likewise together have this meaning or each individually are the said nitriles, in which R₂₈, R₂₉, R₃₀, R₃₁, R₃₂, R₃₃, R₃₄, R₃₅, R₃₆ and R₃₇ independently of one another are hydrogen, methyl, methoxy or phenyl, where, in the case of the groups A₁ and A₂ on adjacent carbon atoms, a benzene ring can be fused on.

Another particularly preferred sub-group of the compounds of the formula IX are those in which L₁, L₂ and L₃ together are monocyclic, polycyclic or fused arenes having 6 to 24, preferably 6 to 18, and particularly preferably 6 to 12 C atoms, which are unsubstituted or substituted by C₁-C₄alkyl, C₁-C₄alkoxy, C₆-C₁₂aryl or halogen, or monocyclic heteroarenes, fused heteroarenes or fused arene-heteroarenes having 4 to 22, preferably 4 to 16, and in particular 4 to 10 C atoms and 1 to 3 heteroatoms chosen from the group consisting of O, S and N, which are unsubstituted or substituted by C₁-C₄alkyl, C₁-C₄alkoxy or halogen, and L₄, L₅ and L₆ are a non-photolabile ligand, the previous preferred meanings also applying here.

In this sub-group, L₁, L₂ and L₃ are preferably benzene or naphthalene, and the non-photolabile ligand is preferably H₂O, NH₃, C₁-C₄alkanol or -alkanethiol which are unsubstituted or substituted by fluorine, aliphatic ethers, thioethers, sulfoxides and sulfones having 2 to 8 C atoms, dimethylformamide or N-methylpyrrolidone.

In another preferred sub-group of compounds of the formula X, the compounds are ruthenium and osmium compounds of the formula X

 [L₁Me(L₈)₅]²⁺[Y₁ ^(x−)]_(2/x)  (X),

in which L₁ is a photolabile ligand and L₈ is a non-photolabile ligand, Me is Ru or Os, Y₁ is a non-coordinating anion and x is the numbers 1, 2 or 3. For the photolabile ligands, non-photolabile ligands, Me and Y₁, the abovementioned preferred meanings apply. Particularly preferably, L₁ is N₂ or a nitrile, for example C₁-C₄alkylnitrile (acetonitrile), benzonitrile or benzylnitrile, L₈ is NH₃ or an amine having 1 to 12 C atoms, Y₁ is a non-coordinating anion and x is the number 1 or 2.

Catalysts which are particularly suitable for the present invention are (tos is tosylate and tis is 2,4,6-triisopropylphenylsulfonate): Ru(CH₃CN)₆(tos)₂, Ru(CH₃CH₂CN)₆(tos)₂, Ru(CH₃CN)₆(CF₃SO₃)₂, Ru(CH₃CH₂CN)₆(CF₃SO₃)₂, Ru(C₆H₆)₂(tos)₂, [Ru(C₆H₆)(C₆H₅OCH₃)](BF₄)₂, [Ru(C₆H₆)(C₆H₅i-propyl)](BF₄)₂, [Ru(C₆H₆)(1,3,5-trimethylphenol)](BF₄)₂, [Ru(C₆H₆)(hexamethylbenzene)](BF₄) ₂, [Ru(C₆H₆)(biphenyl)](BF₄)₂, [Ru(C₆H₆)(chrysene)](BF₄)₂, [Ru(C₆H₆)(naphthalene)](BF₄)₂, [Ru(cyclopentadienyl)(4-methylcumyl)]PF₆, [Ru(cyanophenyl)₆](tos)₂, [Ru(cyanophenyl)₆](CF₃SO₃)₂, [Ru(C6H₆)(tetramethylthiophene)₃](tos)₂, [Ru(C₆H₆)(CH₃CN)₃](tos)₂, [Ru(C₆H₆)(tetramethylthiophene)₃](CF₃SO₃)₂, [Ru(C₆H₆)(CH₃CN)₃](CF₃SO₃)₂, [Ru(C₆H₆)(CH₃OH)₃](tos)₂, [Ru(C₆H₆)(CH₃OH)₃](tis)₂, [Os(NH₃)₅N₂](PF₆)₂, [Ru(NH₃)₅N₂](PF₆)₂, [Ru(NH₃),(CH₃CN)]BF₄, [Ru(C₆H₆(NH₃) ₃](tis)₂, [Ru(C₆H₆(tetrahydrothiophene)₃](CF₃SO₃)₂, [Ru((CH₃)₂S)₃C₆H₆](tos)₂, [Ru(dimethyl sulfoxide)₃C₆H₆](PF₆)₂, [Ru(dimethylformamide)₃C₆H₆](PF6)₂, [Ru (C₆H₆)Cl₂]₂ and [Os(C₆H₆)Cl₂]₂.

Ruthenium and osmium catalysts to be used according to the invention are either known and in some cases commercially obtainable, or can be prepared analogously to known processes. Such catalysts and their preparation are described, for example, in Gilkerson, W. R., Jackson, M. D., J. Am. Chem. Soc. 101:4096-411 (1979), Bennett, M. A., Matheson, T. W., J. Organomet. Chem. 175:87-93 (1979), Moorehouse, S., Wilkinson, G., J. Chem. Soc.; Dalton Trans., 2187-2190 (1974) and Luo, S., Rauchfuss, T. B., Wilson, S. R., J. Am. Chem. Soc. 114:8515-8520 (1992).

2. Heat-stable molybdenum(VI) or tungsten(VI) compounds which can be activated by heat or with radiation and have at least two methyl groups or two monosubstituted methyl groups bonded to the metal, the substituent having no hydrogen atom in the α position.

The other valencies of the molybdenum- and tungsten are preferably satisfied by heat-stable neutral ligands, a very large number of which are known. The number of neutral ligands may also exceed the stoichiometrically possible number (solyates). Heat stability has been explained above. At temperatures above 50° C., for example 60 to 300° C., these molybdenum and tungsten compounds are also activated by heat.

The molybdenum and tungsten compounds to be used according to the invention can be those which contain one metal atom, or two metal atoms bonded via a single, double or triple bond. The methyl group or monosubstituted methyl group bonded to the metal is bonded at least twice, particularly preferably two to six times, and especially preferably two to four times, as a ligand. This ligand preferably is that of the formula IX

—CH₂—R  (XI),

in which R is H, —CF₃, —SiR₃₈R₃₉R₄₀, —CR₄₁R₄₂R₄₃, or C₆-C₁₆aryl or C₄-C₁₅ heteroaryl having 1 to 3 heteroatoms from the group consisting of O, S and N, which are unsubstituted or substituted by C₁-C₆alkyl or C₁-C₆alkoxy; and

R₄₁, R₄₂ and R₄₃ independently of one another are C₁-C₁₀alkyl, which is unsubstituted or substituted by C₁-C₁₀alkoxy, or R₄₁ and R₄₂ have this meaning and R₄₃ is C₆-C₁₀aryl or C₄-C₉heteroaryl, which is unsubstituted or substituted by C₁-C₆alkyl or C₁-C₆alkoxy; and

R₃₈, R₃₉ and R₄₀ are as defined above.

Alkyl R₃₈ to R₄₃ can be linear or branched and preferably contain 1 to 8, and particularly preferably 1 to 4 C atoms. Aryl R₃₈ to R₄₃ is preferably phenyl or naphthyl.

Aryl R in formula XI is preferably phenyl or naphthyl. Heteroaryl R in formula XI is preferably pyridinyl, furanyl, thiophenyl or pyrrolyl.

Preferred substituents for R₃₈ to R₄₃ in the context of the definitions are methyl, ethyl, methoxy and ethoxy. Examples of the radicals R₃₈ to R₄₃ have been given above under the compounds of the formula I.

In a preferred embodiment, the group R in formula XI is H, —C(CH₃)₃, —(CH₃)₂C₆H₅, phenyl which is unsubstituted or substituted by methyl, ethyl, methoxy or ethoxy, —CF₃, or —Si(CH₃)₃.

The other valencies of the Mo(VI) and W(VI) atoms may be satisfied by identical or different ligands from the group consisting of ═O, ═N—R₄₄, secondary amines having 2 to 18 C atoms, R₄₅O—, R₄₅S—, halogen, unsubstituted or substituted cyclopentadienyl, bridged biscyclopentadienyl, tridentate monoanionic ligands and neutral ligands, for example ethers, nitriles, CO and tertiary phosphines and amines, in which the R₄₅ independently of one another are linear or branched C₁-C₁₈alkyl which is unsubstituted or substituted by C₁-C₆alkoxy or halogen, C₅- or C₆cycloalkyl which is unsubstituted or substituted by C₁-C₆alkyl, C₁-C₆alkoxy or halogen, phenyl which is unsubstituted or substituted by C₁-C₆alkyl, C₁-C₆alkoxy, C₁-C₆alkoxymethyl, C₁-C₆alkoxyethyl or halogen, or benzyl or phenylethyl which are unsubstituted or substituted by C₁-C₆alkyl, C₁-C₆alkoxy, C₁-C₆alkoxymethyl, C₁-C₆alkoxyethyl or halogen; and R₄₄ is linear or branched C₁-C₁₈alkyl which is unsubstituted or substituted by C₁-C₆alkoxy, C₅- or C₆cycloalkyl which is unsubstituted or substituted by C₁-C₆alkyl, C₁-C₆alkoxy or halogen, phenyl which is unsubstituted or substituted by C₁-C₆alkyl, C₁-C₆alkoxy, C₁-C₆alkoxymethyl, C₁-C₆alkoxyethyl, di(C₁-C₆alkyl)amino, di(C₁-C₆alkyl)amino-C₁-C₃alkyl or halogen, or benzyl or phenylethyl which are unsubstituted or substituted by C₁-C₆alkyl, C₁-C₆alkoxy, C₁-C₆alkoxymethyl, C₁-C₆alkoxyethyl or halogen.

Secondary amines are preferably those of the formula R₄₆R₄₇N—, in which R₄₆ and R₄₇ independently of one another are linear or branched C₁-C₁₈alkyl; C₅- or C₆cycloalkyl; benzyl or phenylethyl which are unsubstituted or substituted by C₁-C₆alkoxy, or halogen, or (C₁-C₆alkyl)₃Si; or R₄₆ and R₄₇ together are tetramethylene, pentamethylene or 3-oxapentane-1,5-diyl. The alkyl preferably contains 1 to 12, and particularly preferably 1 to 6 C atoms. Some examples are dimethyl-, diethyl-, di-n-propyl-, di-i-propyl-, di-n-butyl-, methylethyl-, dibenzyl-, benzylmethyl-, diphenyl-, phenyl-methylamino and di(trimethylsilyl)amino.

Halogen as a ligand or substituent is preferably F or Cl, and particularly preferably Cl.

The cyclopentadienyl can be unsubstituted or substituted by one to five C₁-C₄alkyl, in particular methyl, or —Si(C₁-C₄alkyl), in particular —Si(CH₃)₃. Bridged cyclopentadienyls are, in particular, those of the formula R₄₈—A—R₄₈, in which R₄₈ is cyclopentadienyl which is unsubstituted or substituted by one to five C₁-C₄alkyl, in particular methyl, or —Si(C₁-C₄alkyl), in particular —Si(CH₃)₃, and A is —CH₂—, —CH₂—CH₂—, —Si(CH₃)₂—, —Si(CH₃)₂—Si(CH₃)₂— or —Si(CH₃) ₂—O—Si(CH₃)₂—.

Ethers as neutral ligands can be dialkyl ethers having 2 to 8 C atoms or cyclic ethers with 5 or 6 ring members. Some examples are diethyl ether, methyl ethyl ether, diethyl [sic] ether, di-n-propyl ether, di-i-propyl ether, di-n-butyl ether, ethylene glycol dimethyl ether, tetrahydrofuran and dioxane.

Nitriles as neutral ligands can be aliphatic or aromatic nitriles having 1 to 12, preferably 1 to 8 C atoms. Some examples are acetonitrile, propionitrile, butylnitrile, benzonitrile and benzylnitrile.

Tertiary amines and phosphines as neutral ligands can be those having 3 to 24, preferably 3 to 18 C atoms. Some examples are trimethylamine and -phosphine, triethylamine and -phosphine, tri-n-propylamine and -phosphine, tri-n-butylamine and -phosphine, triphenylamine and -phosphine, tricyclohexylamine and -phosphine, phenyldimethylamine and -phosphine, benzyldimethylamine and -phosphine, 3,5-dimethylphenyl-dimethylamine and -phosphine.

The tridentate monoanionic ligands can be, for example, hydro(tris-pyrazol-1-yl)borates or alkyl(trispyrazol-1-yl)borates, which are unsubstituted or substituted by one to three C₁-C₄alkyl [see Trofimenko, S., Chem. Rev., 93:943-980 (1993)], or [C₅(R′₅)Co(R₅₀R₅₀ R₅₁P═O)₃]⁻, in which R′ is H or methyl and R₅₀ and R₅₁ independently of one another are C₁-C₄alkyl, C₁-C₄alkoxy or phenyl [see Kläui, W., Angew. Chem. 102:661-670 (1990)].

Halogen as a substituent for the radicals R₄₄ and R₄₅ is preferably fluorine, and particularly preferably chlorine. The substituents alkyl, alkoxy or alkoxy in alkoxymethyl or -ethyl preferably contain 1 to 4, and in particular 1 or 2 C atoms. Examples are methyl, ethyl, n- and i-propyl, n-, i- and t-butyl, methoxy, ethoxy, n- and i-propyloxy and n-, i- and t-butyloxy.

Alkyl R₄₄ and R₄₅ preferably contain 1 to 12, particularly preferably 1 to 8, and especially preferably 1 to 4 C atoms. The alkyl is preferably branched alkyl. Some examples of R₄₄ are methoxy, ethoxy, n- and i-propyloxy, n-, i- and t-butyloxy, hexafluoro-i-propyloxy and hexa- and perfluorobutyloxy.

Some examples of substituted phenyl and benzyl R₄₄ and R₄₅ are p-methylphenyl or benzyl, p-fluoro- or p-chlorophenyl or -benzyl, p-ethylphenyl or -benzyl, p-n- or i-propylphenyl or -benzyl, p-i-butylphenyl or -benzyl, 3-methylphenyl or -benzyl, 3-i-propylphenyl or -benzyl, 2,6-dimethylphenyl or -benzyl, 2,6-di-i-propylphenyl or -benzyl, 2,6-di-n- or -t-butylphenyl and -benzyl. R₄₅ is particularly preferably phenyl which is unsubstituted or substituted by C₁-C₄alkyl or C₁-C₄alkoxy.

In a preferred embodiment, the molybdenum and tungsten compounds are, in particular, those of one of the formulae XII to XIIc

in which

Me is Mo(VI) or W(VI);

at least two, preferably 2 to 4, of the radicals R₅₃ to R₅₈ are a radical —CH₂—R of the formula XI in which R is as defined above;

in each case two of the other radicals of R₅₃ to R₅₈ are ═O or ═N—R₄₄, and R₄₄ is as defined above; and/or

the other radicals of R₅₃ to R₅₈ are secondary amino having 2 to 18 C atoms, R₄₅O— or R₄₅S—, halogen, cyclopentadienyl or bridged biscyclopentadienyl or a neutral ligand, in which R₄₅ is as defined above. For the radicals R, R₄₄ and R₄₅, the abovementioned preferred meanings apply.

In a particularly preferred embodiment, molybdenum or tungsten compounds of the formula XII which are employed in the composition according to the invention are those in which

a) R₅₃ to R₅₈ are a radical of the formula XI —CH₂—R, or

b) R₅₃ and R₅₄ are a radical of the formula XI —CH₂—R, R₅₅ and R₅₆ together are the radical ═N—R₄₄, and R₅₇ and R₅₈ together independently of one another are R₄₅—O— or halogen, or

c) R₅₃ and R₅₄ together and R₅₅ and R₅₆ together are the radical ═N—R₄₄, and R₅₇ and R₅₈ are a radical of the formula XI —CH₂—R,

in which R, R₄₄ and R₄₅ have the above meanings. For R, R₄₄ and R₄₅, the above preferred meanings apply.

Particularly preferred compounds of the formula XIIc are those in which R₅₃, R₅₄ and R₅₅ are a radical of the formula XI, the radical of the formula XI particularly preferably being —CH₂—Si(C₁-C₄alkyl)₃.

Molybdenum or tungsten compounds which are especially preferably used in the composition according to the invention are those of the formulae XIII, XIIIa or XIIIb

in which

Me is Mo(VI) or W(VI),

R is H, —C(CH₃)₃, —C(CH₃)₂—C₆H₅, —C₆H₅ or —Si(C₁-C₄alkyl)₃,

R₆₃ is phenyl or phenyl which is substituted by 1 to 3 C₁-C₄alkyl or C₁-C₄alkoxy,

R₅₃ is linear or branched C₁-C₄alkoxy which is unsubstituted or substituted by fluorine, and

R₅₄ has the same meaning as R₅₃ or is F, Cl or Br. R₅₃ is particularly preferably branched alkoxy, which is unsubstituted or partly or completely substituted by F, for example i-propyloxy, i- and t-butyloxy, hexafluoropopyloxy [sic] and nonafluoropropyloxy. R₅₄ is preferably Cl.

Some examples of molybdenum and tungsten compounds are: W(═N—C₆H₅)(OC(CH₃)₃)(Cl)[(CH₂Si(CH₃)₃)]₂, [(CH₃)₃SiCH₂]₃Mo≡Mo[CH₂Si(CH₃)₃]₃, W(═N—C₆H₅)(OC(CF₃)₂CH₃)₂[(CH₂Si(CH₃)₃)]₂, W(═NC₆H₅)[CH₂Si(CH₃)₃]₃Cl, Mo(═N-2,6-dimethylC₆H₅)₂[(CH₂—C₆H₅)]₂, W[2,6-(CH₃) ₂C₆H₃N]₂(CH₂—C₆H₅)₂, Mo(═N-2,6-diisopropylC₆H₃)₂[(CH₂—C₆H₅)]₂, Mo(═N-2,6-diisopropylC₆H₃)₂[(CH₂C(CH₃)₂—C₆H₅)]₂ and Mo(═N-2,6-dimethylC₆H₃)₂(CH₃)₂(tetrahydrofuran).

The molybdenum and tungsten catalysts to be used according to the invention are known or can be prepared by known and analogous processes starting from the metal halides by means of Grignard reactions [see, for example, Huq, F., Mowat, W., Shortland, A., Skapski, A. C., Wilkinson, G., J. Chem. Soc., Chem. Commun. 1079-1080 (1971) or Schrock, R. R., Murdzeck, J. S., Bazan, G. C., Robbins, J., DiMare, M., O'Regan, M., J. Am. Chem. Soc., 112:3875-3886 (1990)].

3. Heat-stable titanium(IV), niobium(V), tantalum(V), molybdenum(VI) or tungsten(VI) compounds in which a silylmethyl group and at least one halogen are bonded to the metal. These one-component catalysts are particularly photocatalytically active.

The titanium(IV), niobium(V) and tantalum(V) compounds to be used according to the invention are those which contain one metal atom. The molybdenum(VI) and tungsten(VI) compounds to be-used according to the invention can be those which contain one metal atom, or two metal atoms bonded via a single, double or triple bond. The other valencies of the titanium, niobium, tantalum, molybdenum and tungsten are preferably satisfied by heat-stable neutral ligands, the definition of heat stability having been given above. The halogen bonded to the metal atom is preferably F, Cl, Br and I more preferably F, Cl and Br, and particularly preferably F or Cl. The silylmethyl ligand preferably corresponds to the formula XIV

—CH₂—SiR₃₈R₃₉R₄₀  (XIV),

in which

R₃₈, R₃₉ and R₄₀ independently of one another are C₁-C₁₈alkyl, C₅- or C₆cycloalkyl or phenyl or benzyl which are unsubstituted or substituted by C₁-C₆alkyl or C₁-C₆alkoxy.

Alkyl R₃₈ to R₄₀ can be linear or branched and preferably contains 1 to 12, particularly preferably 1 to 8, and in particular 1 to 4 C atoms. The particularly preferred alkyl is methyl and ethyl.

Preferred substituents for phenyl and benzyl R₃₈ to R₄₀ in the context of the definitions are methyl, ethyl, methoxy and ethoxy.

In a preferred embodiment R₃₈ to R₄₀ in the group of formula XIV are C₁-C₄alkyl, phenyl or benzyl.

Some examples of the group of the formula XIV are —CH₂—Si(CH₃)₃, —CH₂—Si(C₂H₅)₃, —CH₂—Si(n-C₃H₇)₃, —CH₂—Si(n-C₄H₉)₃, —CH₂—Si(CH₃) ₂(n-C₄H₉), —CH₂—Si(CH₃)₂(t-C₄H₉), —CH₂—Si(CH₃)₂(C₂H₅), —CH₂—Si(CH₃)₂[C(CH₃)₂CH(CH₃)₂], —CH₂—Si(CH₃)₂(n-C₁₂H₂₅), —CH₂—Si(CH₃)₂(n-C₁₈H₃₇), —CH₂—Si(C₆H₅)₃, —CH₂—Si(CH₂—C₆H₅)₃, —CH₂—Si(C₆H₅)(CH₃)₂ and —CH₂—Si(CH₂—C₆H₅)(CH₃)₂ —CH₂—Si(CH₃)₃ is especially preferred.

The other valencies of the Ti(IV), Nb(V), Ta(V), Mo(VI) and W(VI) atoms may be satisfied by identical or different neutral ligands, for example chosen from the group consisting of ═O, ═N—R₄₄, secondary amines having 2 to 18 C atoms, R₄₅O—, R₄₅S—, halogen, substituted or unsubstituted cyclopentadienyl, bridged biscyclopentadienyl, tridentate monoanionic ligands and neutral ligands, for example ethers, nitriles, CO and tertiary phosphines and amines, in which the R₄₅ independently of one another are linear or branched C₁-C₁₈alkyl which is unsubstituted or substituted by C₁-C₆alkoxy or halogen, C₅- or C₆cycloalkyl which is unsubstituted or substituted by C₁-C₆alkyl, C₁-C₆alkoxy or halogen, phenyl which is unsubstituted or substituted by C₁-C₆alkyl, C₁-C₆alkoxy, C₁-C₆alkoxymethyl, C₁-C₆alkoxyethyl or halogen, or benzyl or phenylethyl which are unsubstituted or substituted by C₁-C₆alkyl, C₁-C₆alkoxy, C₁-C₆alkoxymethyl, C₁-C₆alkoxyethyl or halogen; and R₄₄ is linear or branched C₁-C₁₈alkyl which is unsubstituted or substituted by C₁-C₆alkoxy, C₅- or C₆cycloalkyl which is unsubstituted or substituted by C₁-C₆alkyl, C₁-C₆alkoxy or halogen, phenyl which is unsubstituted or substituted by C₁-C₆alkyl, C₁-C₆alkoxy, C₁-C₆alkoxymethyl, C₁-C₆alkoxyethyl, di(C₁-C₆-alkyl)amino, di(C₁-C₆-alkyl)amino-C₁-C₃alkyl or halogen, or benzyl or phenylethyl, which are unsubstituted or substituted by C₁-C6alkyl, C₁-C₆alkoxy, C₁-C₆alkoxymethyl, C₁C₆alkoxyethyl or halogen, with the proviso that in the case of the titanium compounds, the ligand is not ═O or ═N—R₄₄.

The definitions and preferences of R₄₄ and R₄₅, of secondary amines, of halogen as a further ligand on the metal atoms or as substituent, of cyclopentadienyl, ethers, nitriles, tertiary amines and phosphines as neutral ligands and of tridentate monoanionic ligands have been given previously. Likewise given previously were the definitions and preferences of alkyl, akoxy or alkoxy as a substituent in alkoxymethyl or -ethyl.

In a preferred embodiment, the metal compounds are those, in particular, of the formulae XV, XVa or XVb

in which

Me₁ is Mo(VI) or W(VI);

Me₂ is Nb(V) or Ta(V);

one of the radicals R₆₉ to R₇₄ is a radical —CH₂—SiR₃₈R₃₉R₄₀ of the formula XIV;

at least one of the radicals R₆₉ to R₇₄ is F, Cl or Br;

R₃₈, R₃₉ and R₄₀ independently of one another are C₁-C₆alkyl, C₅- or C₆cycloalkyl, or phenyl or benzyl which are unsubstituted or substituted by C₁-C₆alkyl or C₁-C₆alkoxy;

in formula XV two or in each case two, and in formula XVa two of the other radicals of R₆₉ to R₇₄ each together are ═O or ═N—R₄₄, and R₄₄ is linear or branched C₁-C₁₈alkyl which is unsubstituted or substituted by C₁-C₆alkoxy, C₅- or C₆cycloalkyl which is unsubstituted or substituted by C₁-C₆alkyl, C₁-C₆alkoxy or halogen, phenyl which is unsubstituted or substituted by C₁-C₆alkyl, C₁-C₆alkoxy, C₁-C₆alkoxymethyl, C₁-C₆alkoxyethyl, di(C₁-C₆alkyl)amino, di(C₁-C₆alkyl)amino-C₁-C₃alkyl or halogen, or benzyl or phenylethyl which are unsubstituted or substituted by C₁-C₆alkyl, C₁-C₆alkoxy, C₁-C₆alkoxymethyl, C₁-C₆alkoxyethyl, di(C₁-C₆alkyl)amino, di(C₁-C₆alkyl)amino-C₁-C₃alkyl or halogen, and

the other radicals are secondary amino having 2 to 18 C atoms, R₄₅O— or R₄₅S—, halogen, unsubstituted or substituted cyclopentadienyl or bridged biscyclopentadienyl or a neutral ligand, in which the R₄₅ independently of one another are linear or branched C₁-C₁₈alkyl which is unsubstituted or substituted by C₁-C₆alkoxy or halogen, C₅- or C₆cycloalkyl which is unsubstituted or substituted by C₁-C₆alkyl, C₁-C₆alkoxy or halogen, phenyl which is unsubstituted or substituted by C₁-C₆alkyl, C₁-C₆alkoxy, C₁-C₆alkoxymethyl, C₁-C₆alkoxyethyl, di(C₁-C₆-alkyl)amino, di(C₁-C₆-alkyl)amino-C₁-C₃alkyl or halogen, or benzyl or phenylethyl which are unsubstituted or substituted by C₁-C₆alkyl, C₁-C₆alkoxy, C₁-C₆alkoxymethyl, C₁-C₆alkoxyethyl, di(C₁-C₆-alkyl)amino, di(C₁-C₆-alkyl)amino-C₁-C₃alkyl or halogen; or

in the formulae XV, XVa and XVb, the other radicals independently of one another are secondary amino having 2 to 18 C atoms, R₄₅O— or R₄₅S—, halogen, unsubstituted or substituted cyclopentadienyl or bridged biscyclopentadienyl or a neutral ligand, in which the R₄₅ independently of one another are linear or branched C₁-C₁₈alkyl which is unsubstituted or substituted by C₁-C₆alkoxy or halogen, C₅- or C₆cycloalkyl which is unsubstituted or substituted by C₁-C₆alkyl, C₁-C₆alkoxy or halogen, phenyl which is unsubstituted or substituted by C₁-C₆alkyl, C₁-C₆alkoxy, C₁-C₆alkoxymethyl, C₁-C₆alkoxyethyl, di(C₁-C₆-alkyl)-amino, di(C₁-C₆-alkyl)amino-C₁-C₃alkyl or halogen, or benzyl or phenylethyl which are unsubstituted or substituted by C₁-C₆alkyl, C₁-C₆alkoxy, C₁-C₆alkoxymethyl, C₁-C₆alkoxyethyl, di(C₁-C₆-alkyl)amino, di(C₁-C₆-alkyl)amino-C-C₃-alkyl or halogen.

For the radicals R₆₉ to R₇₄, the abovementioned preferred meanings apply.

In a particularly preferred embodiment, metal compounds of the formulae XV, XVa or XVb which are used in the process according to the invention are those in which

R₆₉ is a radical of the formula XIV —CH₂—SiR₃₈R₃₉R₄₀ and R₇₀ is F, Cl or Br; and

(a) in formula XV R₇₁ and R₇₂, and R₇₃ and R₇₄ in each case together are the radical ═N—R₄₄, or R₇₁, and R₇₂ together are the radical ═N—R₄₄, and R₇₃ and R₇₄ independently of one another are unsubstituted or substituted cyclopentadienyl, R₄₅—O— or halogen, or

b) in formula XVa R₇₁ and R₇₂ together are the radical ═N—R₄₄, and R₄₄ is unsubstituted or substituted cyclopentadienyl, R₄₅—O— or halogen, or in formula XVa R₇₁, R₇₂ and R₇₃ independently of one another are unsubstituted or substituted cyclopentadienyl, R₄₅—O— or halogen, or

c) in formula XVb R₇₁ and R₇₂ independently of one another are unsubstituted or substituted cyclopentadienyl, R₄₅—O— or halogen,

in which R₃₈ to R₄₄ have the above meanings. For R₃₈, R₃₉, R₄₀, R₄₄ and R₄₅, the above preferred meanings apply.

Metal compounds which are especially preferably used in the process according to the invention are those of the formulae XVI, XVIa, XVIb, XVIc or XVId

in which

Me₁ is Mo(VI) or W(VI);

Me₂ is Nb(V) or Ta(V);

R₇₅ is —Si(C₁-C₄alkyl)₃;

Z is Cl or Br;

R₆₃ is phenyl or phenyl which is substituted by 1 to 3 C₁-C₄alkyl or C₁-C₄alkoxy,

(a) R₇₃ and R₇₄ in formula XVI together are the group ═NR₆₃ or individually independently of one another are F, Cl, Br, linear or branched C₁-C₄alkoxy which is unsubstituted or substituted by fluorine, phenyloxy which is unsubstituted or substituted by C₁-C₄alkyl or C₁-C₄alkoxy, or cyclopentadienyl which is unsubstituted or substituted by C₁-C₄alkyl;

(b) R₇₁, R₇₂, R₇₃ and R₇₄ in formula XVIa independently of one another are F, Cl, Br, linear or, in particular, branched C₁-C₄-alkoxy which is unsubstituted or substituted by fluorine, phenyloxy which is unsubstituted or substituted by C₁-C₄alkyl or C₁-C₄alkoxy, or cyclopentadienyl which is unsubstituted or substituted by C₁-C₄alkyl;

(c) R₇₃ in formula XVIb is F, Cl, Br, linear or branched C₁-C₄alkoxy which is unsubstituted or substituted by fluorine, phenyloxy which is unsubstituted or substituted by C₁-C₄alkyl or C₁-C₄alkoxy, or cyclopentadienyl which is unsubstituted or substituted by C₁-C₄alkyl;

(d) R₇₁, R₇₂ and R₇₃ in formula XVIc independently of one another are Fl, Cl, Br, linear or, in particular, branched C₁-C₄alkoxy which is unsubstituted or substituted by fluorine, phenyloxy which is unsubstituted or substituted by C₁-C₄alkyl or C₁-C₄alkoxy, or cyclopentadienyl which is unsubstituted or substituted by C₁-C₄alkyl; and

(e) R₇₁ and R₇₂ in formula XVId independently of one another are F, Cl, Br, linear or, in particular, branched C₁-C₄alkoxy which is unsubstituted or substituted by fluorine, phenyloxy which is unsubstituted or substituted by C₁-C₄alkyl or C₁-C₄alkoxy, or cyclopentadienyl which is unsubstituted or substituted by C₁-C₄alkyl. The alkoxy is particularly preferably branched alkoxy, which is optionally partly or completely substituted by F, for example i-propyloxy, i- and t-butyloxy, hexafluoropopyloxy [sic] and nonafluoropropyloxy. The phenyloxy radical is, in particular, phenyloxy substituted in the 2,6-positions [sic] by C₁-C₄alkyl, for example 2,6-dimethylphenyloxy. Examples of substituted cyclopentadienyl radicals are mono- to pentamethylcyclopentadienyl and trimethylsilylcyclopentadienyl. R₆₃ is preferably phenyl or phenyl which is substituted by C₁-C₁alkyl [sic], in particular phenyl 3,5-dimethyl-, 2,6-dimethyl-, 3,5-diethyl- and 2,6-diethylphenyl.

Especially preferred compounds in the process according to the invention are those of the formulae XVII, XVIIa, XVIIb, XVIc and XVId

(R₆₃—N═)₂Me₁X_(a)CH₂Si(CH₃)₃  (XVII),

(R₆₃—N═)R₇₁Me₁X_(a)(OR₆₂)CH₂Si(CH₃)₃  (XVIIa),

 R₇₂R₇₃Me₂X_(a)(OR₆₂)CH₂Si(CH₃)₃  (XVIIb),

R₆₃—N═Me₂X_(a)(OR₆₂)CH₂Si(CH₃)₃  (XVIIc),

R₇₁—TiX_(a)(OR₆₂)CH₂Si(CH₃)₃  (XVIId),

in which

Me₁ is Mo(VI) or W(VI);

Me₂ is Nb(V) or Ta(V);

Xa is F or Cl;

R₆₃ is phenyl or phenyl which is substituted by 1 or 2 C₁-C₄alkyl groups;

R₆₂ is branched C₃- or C₄alkyl which is unsubstituted or partly or completely substituted by fluorine, or phenyloxy or phenyloxy which is substituted by 1 to 3 methyl or ethyl groups;

R₇₂ and R₇₃ independently of one another are cyclopentadienyl which is unsubstituted by substituted by 1 to 5 methyl groups X_(a) or R₆₂O—; and

R₇₁ which is unsubstituted or substituted by 1 to 5 methyl groups, X_(a) or R₇₂O—.

Some examples of titanium(IV), niobium(V), tantalum(V), molybdenum(VI) and tungsten(VI) compounds are [Cp is cyclpentadienyl and Me is Nb(V) or Ta(V)]: Ti[CH₂Si(CH₃)₃]Cl₃, Ti[CH₂Si(CH₃)₃]Br₃, Cp₂Ti[CH₂Si(CH₃)₃]Cl, (CH₃)₂Ti[CH₂Si(CH₃)₃]Cl, Cp₂Ti[CH₂Si(CH₃)₃]Br, Cp₂Ti[CH₂Si(CH₃)₃]l, CpTi[CH₂Si(CH₃)₃][CH₃]Cl, CpTi[CH₂Si(CH₃)₃]Br₂, [(CH₃)₂CHO]₂Ti[CH₂Si(CH₃)₃]Cl, [(CF₃)₂CHO]₂Ti[CH₂Si(CH₃)₃]Cl, [(CF₃)₂CHO]CpTi[CH₂Si(CH₃)₃]Cl, [(CH₃)₂CHO]CpTi[CH₂Si(CH₃)₃]Cl, (C₆H₅O)CpTi[CH₂Si(CH₃)₃]Cl, (2,6-dimethyl-C₆H₅O)CpTi[CH₂Si(CH₃)₃]Cl, (2,6-dimethyl-₆H₅O)₂Ti[CH₂Si(CH₃)₃]Cl [sic], (2,6-dimethyl-C₆H₅O)Ti[CH₂Si(CH₃)₃]₂Br, [(CH₃)₃CO]CpTi[CH₂Si(CH₃)₃]Cl, [(CF₃)₂(CH₃)CO]CpTi[CH₂Si(CH₃)₃]Cl, Me(═N—C₆H₅)[OCH(CH₃ ₂][(CH₂Si(CH₃)₃]Cl, Cp₂Me[(CH₂Si(CH₃)₃]Cl₂, Me(═N—C₆H₅)[OCH(CF₃)₂][(CH₂Si(CH₃)₃]Cl, Ta[CH₂Si(CH₃)₃]₃Cl₂, Me(═N-2,6-diisopropylC₆H₃)[(CH₂Si(CH₃)₃]Cl, Me(═N-2,6-diisopropylC₆H₃)[(CH₃)₂CHO][(CH₂Si(CH₃)₃]Cl, Me(═N-2,6-dimethylC₆H₃)(2,6-Dimethyl-C₆H₅O)[CH₂Si(CH₃)₃]Cl, Me(═N-2,6-dimethylC₆H₃)((CF₃)₂CHO)[CH₂Si(CH₃)₃]Cl, (═N-2,6-dimethylC₆H₃)CpMe[(CH₂Si(CH₃)₃]Cl, (C₆H₅O)₂CpMe[(CH₂Si(CH₃)₃]Cl, (═N-3,5-dimethylC₆H₃)Me[2,6-dimethylC₆H₃O)][(CH₂Si(CH₃)₃)]Cl, CpMe[OCH(CH₃)₂]₂[(CH₂Si(CH₃)₃]Br, CpMe[OCH(CH₃)₂]₂[(CH₂Si(CH₃)₃]Cl, CpMe[OCH(CF₃)₂]₂[(CH₂Si(CH₃)₃]Cl, Cp₂Me(methyl)[(CH₂Si(CH₃)₃]Cl, Cp₂Me[OCH(CH₃)₂][(CH₂Si(CH₃)₃]Cl, [OCH(CH₃)₂]₂Me[CH₂Si(CH₃)₃]Cl₂, Me(2,6-dimethylphenyloxy)(CH₃O)₂[(CH₂Si(CH₃)₃]Cl, Me[CH₂Si(CH₃)₃][OCH(CH₃)](CF₃O)₂Cl, W(═N—C₆H₅)[(OC(CH₃)₃][CH₂—Si(CH₃)₃]Cl, (2,6-diisopropylphenyloxy)₂Me[CH₂Si(CH₃)₃]Cl₂, CP₂Me[OC(CH₃)₃][(CH₂Si(CH₃)₃]Cl, CpMe[OC(CH₃)(CF₃)₂]₂[(CH₂Si(CH₃)₃]Cl, Mo₂[(CH₂—Si(CH₃)₃)(OCH₂C(CH₃)₃)Cl]₂, Mo(═N-2,6-diisopropylC₆H₃)₂[(CH₂—Si(CH₃)₃]Cl, W(═N—C₆H₅)[(OC(CH₃)₃]₂[CH₂—Si(CH₃)₃]Cl, Mo(═N—C₆H₅)₂[CH₂—Si(CH₃)₃]Cl, Mo(═N-2,6-diisopropylC₆H₃)[(OCH₂C(CH₃)₃]₂[CH₂—Si(CH₃)₃]Cl.

The titanium, niobium, tantalum, molybdenum and tungsten compounds to be used according to the invention are known or can be prepared by known and analogous processes starting from unsubstituted or correspondingly substituted metal halides by means of Grignard reactions [Schrock, R. R., Murdzeck, J. S., Bazan, G. C., Robbins, J., DiMare, M., O'Regan, M., J. Am. Chem. Soc., 112:3875-3886 (1990)].

4. Other suitable photactive one-component catalysts are niobium(V) or tantalum(V) compounds which have at least two methyl groups or two monosubstituted methyl groups bonded to the metal, the substituent containing no hydrogen atom in the α position. These compounds are also thermal catalysts.

The niobium(V) and tantalum(V) compounds to be used according to the invention contain one metal atom. The methyl group or monosubstituted methyl group bonded to the metal is bonded at least twice, particularly preferably two to five times, and especially preferably twice or three times as a ligand. This ligand preferably is that of the formula XI

—CH₂—R  (XI),

in which R has the meanings and preferred meanings given above.

The other valencies of the niobium and tantalum atom are preferably satisfied by heat-stable neutral ligands, a very large number of which are known. The number of neutral ligands may also exceed the stoichiometrically possible number (solyates). The definition of heat stability has been given above.

The other valencies of the Nb(V) and Ta(V) atoms may be satisfied by identical or different neutral ligands, for example chosen from the group consisting of =O, ═N—R₄₄, secondary amines having 2 to 18 C atoms, R₄₅O—, R₄₅S—, halogen, unsubstituted or substituted cyclopentadienyl, bridged biscyclopentadienyl, tridentate monoanionic ligands and neutral ligands, for example ethers, nitriles, CO and tertiary phosphines and amines, in which the R₄₅ independently of one another are linear or branched C₁-C₁₈alkyl which is unsubstituted or substituted by C₁-C₆alkoxy or halogen, C₅- or C₆cycloalkyl which is unsubstituted or substituted by C₁-C₆alkyl, C₁-C₆alkoxy or halogen, phenyl which is unsubstituted or substituted by C₁-C₆alkyl, C₁-C₆alkoxy, C₁-C₆alkoxymethyl, C₁-C₆alkoxyethyl or halogen, or benzyl or phenylethyl which are unsubstituted or substituted by C₁-C₆alkyl, C₁-C₆alkoxy, C₁-C₆alkoxymethyl, C₁-C₆-alkoxyethyl or halogen; and R_(44,) is linear or branched C₁-C₁₈alkyl which is unsubstituted or substituted by C₁-C₆alkoxy, C₅- or C₆cycloalkyl which is unsubstituted or substituted by C₁-C₆alkyl, C₁-C₆alkoxy or halogen, phenyl which is unsubstituted or substituted by C₁-C₆alkyl, C₁-C₆alkoxy, C₁-C₆alkoxymethyl, C₁-C₆alkoxyethyl, di(C₁-C₆-alkyl)-amino, di(C₁-C₆alkyl)amino-C₁-C₃alkyl, or halogen, or benzyl or phenylethyl which are unsubstituted or substituted by C₁-C₆alkyl, C₁-C₆alkoxy, C₁-C₆alkoxymethyl, C₁-C₆alkoxyethyl or halogen.

The definitions and preferences of R₄₄ and R₄₅, of secondary amines, of halogen as a further ligand on the metal atoms or as substituent, of cyclopentadienyl, ethers, nitriles, tertiary amines and phosphines as neutral ligands and of tridentate monoanionic ligands have been given previously. Likewise given previously were the definitions and preferences of alkyl, alkoxy or alkoxy as a substituent in alkoxymethyl or -ethyl.

In a preferred embodiment, the niobium and tantalum compounds are, in particular, those of the formula XVIII

in which

Me is Nb(V) or Ta(V),

at least two, preferably 2 or 3, of the radicals R₈₂ to R₈₆ are a radical —CH₂—R of the formula XI in which R has the meanings and preferred meanings given above;

two of the other radicals of R₈₂ to R₈₆ together are ═O or ═N—R₄₄, and R₄₄ is linear or branched C₁-C₁₈alkyl which is unsubstituted or substituted by C₁-C₆alkoxy, C₅- or C₆cycloalkyl which is unsubstituted or substituted by C₁-C₆alkyl, C₁-C₆alkoxy or halogen, phenyl which is unsubstituted or substituted by C₁-C₆alkyl, C₁-C₆alkoxy, C₁-C₆alkoxymethyl, C₁-C₆alkoxyethyl, di(C₁-C₆-alkyl) amino, di(C₁-C₆-alkyl)amino-C₁-C₃alkyl or halogen, or benzyl or phenylethyl which are unsubstituted or substituted by C₁-C₆alkyl, C₁-C₆alkoxy, C₁-C₆alkoxymethyl, C₁-C₆alkoxyethyl, di(C₁-C₆-alkyl)amino, di(C₁-C₆alkyl)amino-C₁-C₃alkyl or halogen; and/or

the other radicals of R₈₂ to R₈₆ independently of one another are secondary amino having 2 to 18 C atoms, R₄₅O—, R₄₅S—, halogen, cyclopentadienyl or bridged biscyclopentadienyl or a neutral ligand, in which the R₄₅ independently of one another are linear or branched C₁-C₁₈alkyl which is unsubstituted or substituted by C₁-C₆alkoxy or halogen, C₅- or C₆cycloalkyl which is unsubstituted or substituted by C₁-C₆alkyl, C₁-C₆alkoxy or halogen, phenyl which is unsubstituted or substituted by C₁-C₆alkyl, C₁-C₆alkoxy, C₁-C₆alkoxymethyl, C₁-C₆alkoxyethyl, di(C₁-C₆alkyl)amino, di(C₁-C₆alkyl)amino-C₁-C₃alkyl or halogen, or benzyl or phenylethyl which are unsubstituted or substituted by C₁-C₆alkyl, C₁-C₆alkoxy, C₁-C₆alkoxymethyl, C₁-C₆alkoxyethyl, di(C₁-C₆alkyl)amino, di(C₁-C₆alkyl)amino-C₁-C₃alkyl or halogen.

In a particularly preferred embodiment, the niobium and tantalum compounds of the formula XVIII used are those in which

a) R₈₂ to R₈₆ are each a radical of the formula XI —CH₂—R, or

b) R₈₂ and R₈₃ are each a radical of the formula XI —CH₂—R, R₈₄ and R₈₅ together are the radical ═N—R₄₄, and R₈₆ is unsubstituted or substituted cyclopentadienyl, R₄₅—O— or halogen, or

c) R₈₂, R₈₃ and R₈₄ are each a radical of the formula XI —CH₂—R, and R₈₅ and R₈₆ together are the radical ═N—R₄₄, or [lacuna] R₈₂, R₈₃, R₈₄ and R₈₅ are a radical of the formula XI —CH₂—R, and R₈₆ is unsubstituted or substituted cyclopentadienyl, R₄₅—O— or halogen,

in which R, R₄₄ and R₄₅ have the above meanings. For R, R₄₄ and R₄₅, the above preferred meanings apply.

Niobium and tantalum compounds which are especially preferably used in the process according to the invention are those of the formulae IXX, IXXa or IXXb

in which

Me is Nb(V) or Ta(V),

R_(v) is H, —C(CH₃)₃, —C(CH₃)₂—C₆H₅, —C₆H₅ or —Si(C₁-C₄alkyl)₃,

R₆₃ is phenyl or phenyl which is substituted by 1 to 3 C₁-C₄alkyl or C₁-C₄alkoxy,

R₈₄ in formula IXX is the group —CH₂—R or F, Cl, Br, linear or, in particular, branched C₁-C₄alkoxy which is unsubstituted or substituted by fluorine, phenyloxy which is unsubstituted or substituted by C₁-C₄alkyl or C₁-C₄alkoxy, or cyclopentadienyl which is unsubstituted or substituted by C₁-C₄alkyl;

R₈₂, R₈₃ and R₈₄ in formula IXXa independently of one another are F, Cl, Br, linear or, in particular, branched C₁-C₄alkoxy which is unsubstituted or substituted by fluorine, phenyloxy which is unsubstituted or substituted by C₁-C₄alkyl or C₁-C₄alkoxy, or cyclopentadienyl which is unsubstituted or substituted by C₁-C₄alkyl; and

R₈₂ and R₈₃ in formula IXXb independently of one another are F, Cl, Br, linear or, in particular, branched C₁-C₄alkoxy which is unsubstituted or substituted by fluorine, phenyloxy which is unsubstituted or substituted by C₁-C₄alkyl or C₁-C₄alkoxy, or cyclopentadienyl which is unsubstituted or substituted by C₁-C₄alkyl. The alkoxy is particularly preferably branched alkoxy, which is unsubstituted or completely or partly substituted by F, for example i-propyloxy, i- and t-butyloxy, hexafluoropopyloxy [sic] or nonafluoropropyloxy.

Some examples of niobium(V) and tantalum(V) compounds are [Cp is cyclopentadienyl and Me is Nb(V) or Ta(V)]:

Me[CH₂Si(CH₃)₃]₅, CP₂Me[(CH₂C(CH₃)₂—C₆H₅)]₃, Me(═N-2,6-dimethylC₆H₃)(CH₃)₃,

Me(═N—C₆H₅)[OC(CH₃)₃][(CH₂Si(CH₃)₃)]₂,

Me(═N-2,6-diisopropylC₆H₃)[(CH₂—C₆H₅)]₃,

Me(═N—C₆H₅)[OCCH₃(CF₃)₂][(CH₂Si(CH₃)₃)]₂, CpMe[OCCH₃(CF₃)₂]₂[(CH₂—C₆H₅)]₂,

Me(═N-2,6-diisopropylC₆H₃)[(CH₂C(CH₃)₂—C₆H₅)]₂Cl, Cp₂Me(CH₃)₂[OCH(CH₃)₂],

Me(═N-2,6-dimethylC₆H₃)[(CH₂—C₆H₅)]₃, CpMe[OCH(CH₃)₂]₂[(CH₂Si(CH₃)₃)]₂,

Cp₂Me[(CH₂—C₆H₅)]₃, Me[CH₂Si(CH₃)₃]₃Cl₂, Me[CH₂Si(CH₃)₃]₃[OCH₂C(CH₃)₃]₂,

Cp₂Me[3,5-dimethylC₆H₃O)][CH₂Si(CH₃)₃)]₂, Me(2,6-diisopropylphenyloxy)₂(CH₃)₃,

Cp₂Me(CH₃)₃, Me(2,6-dimethylphenyloxy)₂(CH₃)₃,

Me[CH₂Si(CH₃)₃]₃[OCH(CH₃)]₂, CpMe[OC(CH₃)₃]₂[(CH₂—C₆H₅)]₂ and

Cp₂Me[(CH₂Si(CH₃)₃)]₃.

The niobium and tantalum compounds to be used according to the invention are known or can be prepared by known and analogous processes starting from the optionally substituted metal halides via Grignard reactions and/or substitution reactions [Schrock, R. R., Murdzeck, J. S., Bazan, G. C., Robbins, J., DiMare, M., O'Regan, M., J. Am. Chem. Soc., 112:3875-3886 (1990)].

5. Other suitable photoactive one-component catalysts are titanium(IV) compounds which contain at least two methyl groups or two monosubstituted methyl groups bonded to the metal, the substituent containing no hydrogen atom in the α position. These compounds are also thermal catalysts.

The titanium(IV) compounds to be used according to the invention contain one metal atom. The methyl group or monosubstituted methyl group bonded to the metal is bonded at least twice, particularly preferably two to four times, and especially preferably twice or three times as a ligand. This ligand preferably is that of the formula XI

 —CH₂—R  (XI),

in which R has the abovementioned meanings and preferred meanings.

The other valencies of the titanium atom are preferably satisfied by heat-stable neutral ligands, a large number of which are known. The number of neutral ligands may also exceed the stoichiometrically possible number (solvates). Heat stability has been explained above.

The other valencies of the titanium(IV) atoms may be satisfied by identical or different neutral ligands, for example chosen from the group consisting of secondary amines having 2 to 18 C atoms, R₄₅O—, R₄₅S—, halogen, unsubstituted or substituted cyclopentadienyl, bridged biscyclopentadienyl, tridentate monoanionic ligands and neutral ligands, for example ethers, nitriles, CO and tertiary phosphines and amines, in which the R₄₅ independently of one another are linear or branched C₁-C₁₈alkyl which is unsubstituted or substituted by C₁-C₆alkoxy or halogen, C₅- or C₆cycloalkyl which is unsubstituted or substituted by C₁-C₆alkyl, C₁-C₆alkoxy or halogen, phenyl which is unsubstituted or substituted by C₁-C₆alkyl, C₁-C₆alkoxy, C₁-C₆alkoxymethyl, C₁-C₆alkoxyethyl or halogen, or benzyl or phenylethyl which are unsubstituted or substituted by C₁-C₆alkyl, C₁-C₆alkoxy, C₁-C₆alkoxymethyl, C₁-C₆-alkoxyethyl or halogen.

The definitions and preferences of R₄₅, of secondary amines, of halogen as a further ligand on the metal atoms or as substituent, of cyclopentadienyl, ethers, nitriles, tertiary amines and phosphines as neutral ligands and of tridenate monoanionic ligands have been given previously. Likewise given previously were the definitions and preferences of alkyl, alkoxy or alkoxy as a substituent in alkoxymethyl or -ethyl.

In a preferred embodiment, the titanium(IV) compounds are, in particular, those of the formula XX

in which

at least two, preferably 2 or 3, of the radicals R₈₇ to R₉₀ are a radical —CH₂—R of the formula XI in which R has the abovementioned meanings and preferred meanings; and

the other radicals R₈₇ to R₉₀ are secondary amino having 2 to 18 C atoms, R₄₅O—, R₄₅S—, halogen, cyclopentadienyl or bridged biscyclopentadienyl or a neutral ligand, in which the R₄₅ independently of one another are linear or branched C₁-C₁₈alkyl which is unsubstituted or substituted by C₁-C₆alkoxy or halogen, C₅- or C₆cycloalkyl which is unsubstituted or substituted by C₁-C₆alkyl, C₁-C₆alkoxy or halogen, phenyl which is unsubstituted or substituted by C₁-C₆alkyl, C₁-C₆alkoxy, C₁-C₆alkoxymethyl, C₁-C₆alkoxyethyl, di(C₁-C₆alkyl)amino, di(C₁-C₆alkyl)amino-C₁-C₃alkyl or halogen, or benzyl or phenylethyl which are unsubstituted or substituted by C₁-C₆alkyl, C₁-C₆alkoxy, C₁-C₆alkoxymethyl, C_(1-C) ₆alkoxyethyl, di(C₁-C₆alkyl)amino, di(C₁-C₆alkyl)amino-C₁-C₃alkyl or halogen.

In a particularly preferred embodiment, titanium(IV) compounds of the formula XX which are used in the process according to the invention are those in which

a) R₈₇ to R₉₀ are a radical of the formula XI —CH₂—R, or

b) R₈₇ and R₈₈ are a radical of the formula XI —CH₂—R, and R₈₉ and R₉₀ independently of one another are unsubstituted or substituted cyclopentadienyl, R₄₅—O— or halogen, or

c) R₈₇, R₈₈ and R₈₉ are a radical of the formula XI —CH₂—R, and R₉₀ is unsubstituted or substituted cyclopentadienyl, R₄₅—O— or halogen,

where R and R₄₅ have the above meanings. For R and R₄₅, the above preferred meanings apply.

Titanium(IV) compounds which are especially preferably used in the process according to the invention are those of the formulae XXIa or XXIb

in which

R_(v) is H, —C(CH₃)₃, —C(CH₃)₂—C₆H₅, —C₆H₅ or —Si(C₁-C₄alkyl)₃, and

R₈₇ and R₈₈ independently of one another are F, Cl, Br, linear or, in particular, branched C₁-C₄alkoxy which is unsubstitutued or substituted by fluorine, phenyloxy which is unsubstituted or substituted by C₁-C₄alkyl or C₁-C₄alkoxy, or cyclopentadienyl which is unsubstituted or substituted by C₁-C₄alkyl. The alkoxy is particularly preferably branched alkoxy, which is unsubstituted or partly or completely substituted by F, for example i-propyloxy, i- and t-butyloxy, hexafluoropropyloxy and nonafluoropropyloxy.

In a preferred embodiment of the invention, the titanum(IV) compounds contain a halogen atom, in particular Cl or Br, bonded to the titanium if the radical R in the group —CH₂—R is —SiR₃₈R₃₉R₄₀. In this case, especially preferred compounds are those of the formula XXII

in which

Y₁ is F, Cl or Br,

R₃₈, R₃₉ and R₄₀ independently of one another are C₁-C₁₈alkyl, C₅- or C₆cycloalkyl or phenyl or benzyl which are unsubstituted or substituted by C₁-C₆alkyl or C₁-C₆alkoxy; and

R₈₇ is the group —CH₂—SiR₃₈R₃₉R₄₀, F, Cl, Br, linear or, in particular, branched C₁-C₄alkoxy which is unsubstituted or substituted by fluorine, phenyloxy which is unsubstituted or substituted by C₁-C₄alkyl or C₁-C₄alkoxy, or cyclopentadienyl which is unsubstituted or substituted by C₁-C₄alkyl. R₃₈, R₃₉ and R₄₀ are preferably C₁-C₄alkyl, phenyl or benzyl, and R₈₇ is preferably Cl, C₃- or C₄alkyl which is unsubstituted or substituted by fluorine, or phenyl or benzyl which are unsubstituted or substituted by C₁-C₄alkyl or C₁-C₄alkoxy.

Some examples of titanium(IV) compounds are [Cp is cyclopentadienyl]: Ti[CH₂Si(CH₃)₃]₄, Ti[OCH(CF₃)₂]₂[(CH₂Si(CH₃)₃)]₂, CpTi[(CH₂C(CH₃)₂—C₆H₅)]₂Cl, CpTi[(CH₂—C₆H₅)]₃, TiCl₂[CH₂Si(CH₃)₃)]₂, [OCH(CF₃)₂]Ti[(CH₂—C₆H₅)]₃, CpBrTi[(CH₂C(CH₃)₂—C₆H₅)]₂, CpTi[2,6-dimethylC₆H₃O)][(CH₂Si(CH₃)₃)]₂, Ti[OCH(CH₃)₂]₂[(CH₂—C₆H₅)]₂, ClTi[OCH(CH₃)₂][(CH₂Si(CH₃)₃)]₂, CpTi[OCH(CF₃)₂][(CH₂—C₆H₅)]₂, CpTi(methyl)₃, CpTi(methyl)₂[OCH(CH₃)₂], Ti[CH₂Si(CH₃)₃]₂Br₂, Ti(2,6-dimethylphenyloxy)₂(CH₃)₂, Cp₂Ti(CH₃)₂, Ti[CH₂Si(CH₃)₃]₃[OCH(CH₃)] and Ti(2,6-diisopropylphenyloxy)₂(CH₃)₂.

The titanium(IV) compounds to be used according to the invention are known or can be prepared by known and analogous processes starting from the metal halides via Grignard reactions or other known substitution reactions [see Clauss, K., Bestian, H., Justus Liebigs Ann. Chem. 654:8-19 (1962)].

6. Other suitable photocatalytically active compounds are ruthenium or osmium compounds which contain at least one phosphine group, at least one photolabile ligand and optionally neutral ligands bonded to the metal atom, 2 to 5 ligands in total being bonded, and which contain acid anions for charge balancing. In total in the context of the invention means the sum of the phosphine groups, photolabile ligands and neutral ligands. The neutral ligands are also called non-photolabile ligands. Preferably 2 to 4, and particularly preferably 2 or 3 ligands are bonded in total.

These osmium compounds are also thermally active catalysts. The ruthenium compounds are thermal catalysts if the phosphine group contains no linear alkyl or alkoxy groups, but bulky groups, for example secondary and tertiary alkyl or alkoxy groups (i-propyl, i- and t-butyl), or cycloalkyl groups, or phenyl groups or pheyloxy groups which are unsubstituted or substituted by 1 to 3 C₁-C₄alkyl or -alkoxy.

The phosphine group is preferably tertiary phosphines and phosphites having 3 to 40, more preferably 3 to 30, and particularly preferably 3 to 24 C atoms.

The other valencies of the ruthenium and osmium are preferably satisifed by heat-stable neutral ligands, a very large number of which are known. The number of neutral ligands can also exceed the stoichiometrically possible number (solvates).

The ruthenium and osmium compounds to be used according to the invention can contain a monophosphine bonded one to three times, and preferably two or three times, and a diphosphine bonded once to the metal atom. Preferably 1 to 2 photolabile ligands are bonded in the ruthenium and osmium catalysts. The phosphine ligands preferably are those of the formulae XXIII and XXIIIa

PR₉₁R₉₂R₉₃  (XXIII)

R₉₁R₉₂P—Z₁—PR₉₁R₉₂  (XXIIIa)

in which R₉₁, R₉₂ and R₉₃ independently of one another are H, C₁-C₂₀alkyl, C₁-C₂₀alkoxy, C₄-C₁₂cycloalkyl or cycloalkoxy which are unsubstituted or substituted by C₁-C₆alkyl, C₁-C₆haloalkyl or C₁-C₆alkoxy or C₆-C₁₆aryl or C₆-C₁₆aryloxy which are unsubstituted or substituted by C₁-C₆alkyl, C₁-C₆haloalkyl or C₁-C₆alkoxy, or C₇-C₁₆aralkyl or C₇-C₁₆aralkyloxy which are unsubstituted or substituted by C₁-C₆alkyl, C₁-C₆haloalkyl or C₁-C₆alkoxy; the radicals R₉₁ and R₉₂ together are tetra- or pentamethylene or tetra- or pentamethylenedioxyl which are unsubstituted or substituted by C₁-C₆alkyl, C₁-C₆haloalkyl or C₁-C₆alkoxy, or tetra- or pentamethylene or tetra- or pentamethylenedioxyl which are unsubstituted or substituted by C₁-C₆alkyl, C₁-C₆haloalkyl or C₁-C₆alkoxy and fused with 1 or 2 1,2-phenylene, or tetramethylenedioxyl which is unsubstituted or substituted by C₁-C₆alkyl, C₁-C₆haloalkyl or C₁C₆alkoxy and is fused in the 1,2- and 3,4-positions with 1,2-phenylene, and R₉₃ has the abovementioned meaning; and Z₁ is linear or branched C₂-C₁₂alkylene which is unsubstituted or substituted by C₁-C₄alkoxy, 1,2- or 1,3-cycloalkylene having 4 to 8 C atoms, which is unsubstituted or substituted by C₁-C₄alkyl or C₁-C₄alkoxy, or 1,2- or 1,3-heterocycloalkylene having 5 or 6 ring members and one heteroatom from the group consisting of O or N, which is unsubstituted or substituted by C₁-C₄alkyl or C₁-C₄alkoxy.

The radicals R₉₁, R₉₂ and R₉₃ are preferably identical radicals.

If R₉₁, R₉₂ and R₉₃ are substituted, the substituents are preferably C₁-C₄alkyl, C₁-C₄haloalkyl or C₁-C₄alkoxy. Halogen is preferably Cl, and particularly preferably F. Examples of preferred substituents are methyl, methoxy, ethyl, ethoxy and trifluoromethyl. R₉₁, R₉₂ and R₉₃ are preferably substituted by 1 to 3 substituents.

Alkyl R₉₁, R₉₂ and R₉₃ can be linear or branched and can preferably contain 1 to 12, more preferably 1 to 8, and particularly preferably 1 to 6 C atoms. Examples of alkyl are methyl, ethyl, n- and i-propyl, n-, i- and t-butyl, the isomers of pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl and eicosyl. Preferred examples are methyl, ethyl, n- and i-propyl, n-, i- and t-butyl, 1-, 2- or 3-pentyl and 1-, 2-, 3- or 4-hexyl.

Alkoxy R₉₁, R₉₂ and R₉₃ can be linear or branched and can preferably contain 1 to 12, more preferably 1 to 8, and particularly preferably 1 to 6 C atoms. Examples of alkoxy are methoxy, ethoxy, n- and i-propyloxy, n-, i- and t-butyloxy, the isomers of pentyloxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy, undecyloxy, dodecyloxy, tridecyloxy, tetradecyloxy, pentadecyloxy, hexadecyloxy, heptadecyloxy, octadecyloxy and eicosyloxy. Preferred examples are methoxy, ethoxy, n- and i-propyloxy, n-, i- and t-butyloxy, 1-, 2- or 3-pentyloxy and 1-, 2-, 3- or 4-hexyloxy.

Cycloalkyl R₉₁, R₉₂ and R₉₃ are preferably C₅-C₈cycloalkyl, and particularly preferably C₅- or C₆cycloalkyl. Some examples are cyclobutyl, cycloheptyl, cyclooctyl and, in particular, cyclopentyl and cyclohexyl. Examples of substituted cycloalkyl are methyl-, dimethyl-, trimethyl-, methoxy-, dimethoxy-, trimethoxy-, trifluoromethyl-, bistrifluoromethyl and tristrifluoromethylcyclopentyl and -cyclohexyl.

Cycloalkyloxy R₉₁, R₉₂ and R₉₃ are preferably C₁-C₈cycloalkyloxy, and particularly preferably C₅- or C₆cycloalkyloxy. Some examples are cyclobutyloxy, cycloheptyloxy, cyclooctyloxy and, in particular, cyclopentyloxy and cyclohexyloxy. Examples of substitued cycloalkyl are methyl-, dimethyl-, trimethyl-, methoxy-, dimethoxy-, trimethoxy-, trifluoromethyl-, bistrifluoromethyl and tristrifluoromethylcyclopentyloxy and -cyclohexyloxy.

Aryl R₉₁, R92 and R₉₃ are preferably C₆-C₁₂aryl and particularly preferably phenyl or naphthyl. Examples of substituted aryl are methyl-, dimethyl-, trimethyl-, methoxy-, dimethoxy-, trimethoxy-, trifluoromethyl-, bistrifluoromethyl and tristrifluoromethylphenyl.

Aryloxy R₉₁, R₉₂ and R₉₃ are preferably C₆-C₁₂aryloxy, and particularly preferably unsubstituted or substituted phenyloxy or naphthyloxy. Examples of substituted aryloxy are methyl-, dimethyl-, trimethyl-, methylisopropyl-, isopropyl-, diisopropyl-, triisopropyl-, tert-butyl-, methyl-tert-butyl-, di-tert-butyl-, tri-tert-butyl-, methoxy-, dimethoxy-, trimethoxy-, trifluoromethyl-, bistrifluoromethyl and tristrifluoromethylphenyloxy.

Aralkyl R₉₁, R₉₂ and R₉₃ are preferably C₇-C₁₃aralkyl, the alkylene group in the aralkyl preferably being methylene. The aralkyl is particularly preferably benzyl. Examples of substituted aralkyl are methyl-, dimethyl-, trimethyl-, methoxy-, dimethoxy-, trimethoxy-, trifluoromethyl-, bistrifluoromethyl and tristrifluoromethylbenzyl.

Aralkyloxy R₉₁, R₉₂ and R₉₃ are preferably unsubstituted or substituted C₇-C₁₃aralkyloxy, the alkylene group in the aralkyloxy preferably being methylene. The aralkyloxy is particularly preferably unsubstituted or substituted benzyloxy. Examples of substituted aralkyloxy are methyl-, dimethyl-, trimethyl-, methoxy-, dimethoxy-, trimethoxy-, trifluoromethyl-, bistrifluoromethyl and tristrifluoromethylbenzyloxy.

Examples of tetra- and pentamethylene which are bonded to the P atom and are unsubstituted or substituted or fused are

Other suitable phosphines are cycloaliphatics having 6 to 8 ring carbon atoms which are bridged with a ═PRa group, for example

in which Ra is C₁-C₆alkyl, cyclohexyl, benzyl, or phenyl which is unsubstituted or substitued by 1 or 2 C₁-C₄alkyl.

Linear or branched alkylene Z₁ is preferably 1,2-alkylene or 1,3-alkylene having preferably 2 to 6 C atoms, for example ethylene, 1,2-propylene or 1,2-butylene.

Examples of cycloalkylene Z₁ are 1,2- and 1,3-cyclopentylene and 1,2- or 1,3-cyclohexylene. Examples of heterocycloalkylene Z₁ are 1,2- and 1,3-pyrrolidine, 1,2- and 1,3-piperidine, and 1,2- and 1,3-tetrahydrofuran.

In a preferred embodiment, the phosphine ligands are those of the formula XXIII in which R₉₁, R₉₂ and R₉₃ independently of one another are H, C₁-C₆alkyl, cyclopentyl or cyclohexyl which are unsubstituted or substituted by C₁-C₄alkyl, or phenyl which are unsubstituted or substituted by C₁-C₄alkyl, C₁-C₄alkoxy or trifluoromethyl, or benzyl which is unsubstituted or substituted by C₁-C₄alkyl, C₁-C₄alkoxy or trifluoromethyl. Particularly preferred examples of phosphine ligands of the formula XXIII are (C₆H₅)₃P, (C₆H₅CH₂)₃P, (C₅H₁₁)₃P, (CH₃)₃P, (C₂H₅)₃P, (n-C₃H₇)₃P, (i-C₃H₇)₃P, (n-C₄H₉)₃P, (C₆H₅)₂HP, (C₆H₅CH₂)₂HP, (C₅H₁₁)₂HP, (C₂H₅)₂HP, (n-C₃H₇)₂HP, (i-C₃H₇)₂HP, (n-C₄H₉)₂HP, (C₆H₅)H₂P, (n-C₄H₉)H₂P, (C₆H₅CH₂)H₂P, (C₅H₁₁)H₂P, (CH₃)H₂P, (CH₃)₂HP, (C₂H₅)H₂P, (n-C₃H₇)H₂P, (i-C₃H₇)H₂P, PH₃, (2-methyl-C₆H₄)₃P, (3—CH₃—C₆H₄)₃P, (4-C₂H₅—C₆H₄)₃P, (4-CH₃—C₆H₄)₃P, (2,4-di-CH₃—C₆H₃)₃P, (2,6-di-CH₃—C₆H₃)₃P, (2-C₂H₅—C₆H₄)₃P, (3-C₂H₅—C₆H₄)₃P, (2-n-C₃H₇—C₆H₄)₃P, (3-n-C₃H₇—C₆H₄)₃P, (4-n-C₃H₇—C₆H₄)₃P, (2-i-C₃H₇—C₆H₄)₃P, (3-i-C₃H₇—C₆H₄)₃P, (4-i-C₃H₇—C₆H₄)₃P, (2-n-C₄H₉—C₆H₄)₃P, (3-n-C₄H₉—C₆H₄)₃P, (4-n-C₄H₉—C₆H₄)₃P, (2-i-C₄H₉—C₆H₄)₃P, (3-i-C₄H₉—C₆H₄)₃P, (4-i-C₄H₉—C₆H₄)₃P, (2-t-C₄H₉—C₆H₄)₃P, (3-t-C₄H₉—C₆H₄)₃P, (4-t-C₄H₉—C₆H₄)₃P, (2-CH₃-6-t-C₄H₉—C₆H₃)₃P, (3-CH₃-6-t-C₄H₉—C₆H₃)₃P, (3-CH₃-6-t-C₄H₉—C₆H₃)₃P, (2,6-di-t-C₄H₉—C₆H₃)₃P, (2,3-di-t-C₄H₉—C₆H₃)₃P, (C₆H₁₁)₃P, (C₆H₁₁)₂HP, (C₅H₉)P, (C₅H₉)₂HP and (2,4-di-t-C₄H₉—C₆H₃)₃P.

In another preferred embodiment, the phosphine ligands correspond to the formula XXIII in which R₉₁, R₉₂ and R₉₃ independently of one another are H, C₁-C₆alkoxy, cyclopentyloxy or cyclohexyloxy which is unsubstituted or substituted by C₁-C₄alkyl, phenyloxy or phenyl which is unsubstituted or substituted by C₁-C₄alkyl, C₁-C₄alkoxy or trifluoromethyl, or benzyloxy which is unsubstituted or substituted by C₁-C₄alkyl, C₁-C₄alkyl, C₁-C₄alkoxy or trifluoromethyl.

Examples of phosphites are (CH₃O)₃P, (C₂H₅O)₃P, (n-C₃H₇O)₃P, (i-C₃H₇O)₃P, (n-C₄H₉O)₃P, (i-C₄H₉O)₃P, (t-C₄H₉O)₃P, (C₆H₅O)₃P, (3-CH₃-6-t-C₄H₉—C₆H₃O)₃P, (2-CH₃—C₆H₄O)₃P, (3-CH₃—C₆H₄O)₃P, (4-CH₃—C₆H₄O)₃P, (2,4-di-CH₃—C₆H₃O)₃P, (2,6-di-CH₃—C₆H₃O)₃P, (2-C₂H₅—C₆H₄O)₃P, (3-C₂H₅—C₆H₄O)₃P, (4-C₂H₅—C₆H₄O)₃P, (2-n-C₃H₇—C₆H₄O)₃P, (3-n-C₃H₇—C₆H₄O)₃P, (4-n-C₃H₇—C₆H₄O)₃P, (2-i-C₃H₇—C₆H₄O)₃P, (3-i-C₃H₇—C₆H₄O)₃P, (4-i-C₃H₇—C₆H₄O)₃P, (2-n-C₄H₉—C₆H₄O)₃P, (3-n-C₄H₉—C₆H₄O)₃P, (4-n-C₄H₉—C₆H₄O)₃P, (2-i-C₄H₉—C₆H₄O)₃P, (3-i-C₄H₉—C₆H₄O)₃P, (4-i-C₄H₉—C₆H₄O)₃P, (2-CH₃-6-t-C₄H₉—C₆H₃O)₃P, (2,3-di-t-C₄H₉—C₆H₃O)₃P, ((2,6-di-t-C₄H₉—C₆H₃O)₃P, 3-t-C₄H₉—C₆H₄O)₃P, (3-CH₃-6-t-C₄H₉—C₆H₃O)₃P, (2,4-di-t-C₄H₉—C₆H₃O)₃P, (4-t-C₄H₉—C₆H₄O)₃P, (2-t-C₄H₉—C₆H₄O)₃P and phosphites of the formula

in which Ra is C₁-C₆alkyl, cyclohexyl, benzyl, or phenyl which is unsubstituted or substituted by 1 or 2 C₁-C₄alkyl.

Particularly preferred phosphines are tri-i-propylphosphine, tri-t-butylphosphine, tricyclopentylphosphine and tricyclohexylphosphine.

Organic or inorganic compounds, atoms or ions which are coordinated to a metal centre are designated as ligands for the ruthenium and osmium compounds to be used according to the invention.

The meanings and preferred meanings of photolabile ligands and non-photolabile ligands (also called highly coordinating ligands) have been mentioned above.

In a preferred embodiment, the Ru and Os catalysts to be used according to the invention contain only photolabile ligands, phosphine groups and anions for charge balancing. The catalysts which are especially preferred are those which contain an arene group as a photolabile ligand, a tertiary phosphine group, and mono- or divalent anions for charge balancing.

Suitable anions of inorganic or organic acids are, for example, hydride (H⁻), halide (for example F⁻, Cl⁻, Br⁻ and I⁻), the anion of an oxygen acid, and BF₄ ⁻, PF₆ ⁻, SbF₆ ⁻ or AsF₆ ⁻. It should be mentioned that the abovementioned cyclopentadienyl is a ligand and anion.

Other suitable anions are C₁-C₂-, preferably C₁-C₆-, and particularly preferably C₁-C₄alcoholates, which, in particular, are branched, for example corresponding to the formula R_(x)R_(y)R_(z)C—O⁻, in which R_(x) is H or C₁-C₁₀alkyl, R_(y) is C₁-C₁₀alkyl and R_(z) is C₁-C₁₀alkyl or phenyl, and the sum of the C atoms of R_(x),R_(y) and R_(z) is 11. Examples are, in particular, i-propyloxy and t-butyloxy.

Other suitable anions are C₃-C₁₈-, preferably C₅-C₁₄- and particularly preferably C₅-C₁₂acetylides, which can correspond to the formula R_(w)—C≡C⁻, in which R_(w) is C₁-C₁₆alkyl, preferably α-branched C₃-C₁₂alkyl, for example of the formula R_(x)R_(y)R_(z)C—, or are [sic] phenyl or benzyl which are unsubstituted or substituted by 1 to 3 C₁-C₄alkyl or C₁-C₄alkoxy. Some examples are i-propyl-, i- and t-butyl-, phenyl-, benzyl-, 2-methyl-, 2,6-dimethyl-, 2-i-propyl-, 2-i-propyl-6-methyl-, 2-t-butyl-, 2,6-di-t-butyl- and 2-methyl-6-t-butylphenylacetylide.

The meanings and preferred meanings of anions of oxygen acids have been mentioned above. H⁻, F⁻, Cl⁻, Br⁻, BF₄ ⁻, PF₆ ⁻, SbF₆ ⁻, AsF₆ ⁻, CF₃SO₃ ⁻, C₆H₅—SO₃ ⁻, 4-methyl-C₆H₅—SO₃; 2,6-dimethyl-C₆H₅—SO₃ ⁻, 2,4,6-trimethyl-C₆H₅—SO₃ ⁻ and 4-CF₃—C₆H₅—SO₃ ⁻ and cyclopentadienyl (Cp⁻) are particularly preferred.

The number of the non-photolabile ligands depends on the number of the phosphine groups, the size of the non-photolabile ligands and the number of photolabile ligands.

In a preferred embodiment, the ruthenium and osmium compounds are particularly preferably those of one of the formulae XXIV to XXIVf

R₉₇L₈Me²⁺(Z^(n−))_(2/n)  (XXIV),

R₉₇L₉L₁₀Me²⁺(Z^(n−))_(2/n)  (XXIVa),

(R₉₇)₂L₉Me²⁺(Z^(n−))_(2/n)  (XXIVb),

(R₉₇ ⁻)₃L₉Me²⁺(Z^(n−))_(2/n)  (XXIVc),

 R₉₇L₈L₉Me²⁺(Z^(n−))_(2/n)  (XXIVd),

R₉₇L₉L₉Me²⁺(Z^(n−))_(2/n)  (XXIVe),

R₉₇L₈L₁₀Me²⁺(Z^(n−))_(2/n)  (XXIVf),

in which

R₉₇ is a tertiary phosphine of the formula XXIII or XXIIIa;

Me is Ru or Os;

n is the numbers 1, 2 or 3;

Z is the anion of an inorganic or organic acid;

(a) L₈ is an arene or heteroarene ligand;

(b) L₉ is a monovalent photolabile ligand which is different to L₈; and

(c) L₁₀ is a monovalent non-photolabile ligand.

For R₉₇, L₈, L₉ and L₁₀, the preferred meanings mentioned above for the individual meanings apply.

In the formulae XXIV to XXIVf, n is preferably 1 or 2, and especially 1. For R₉₇, the preferred meanings mentioned for the phosphine ligands of the formula XXIII apply, and these are, in particular, tertiary phosphines.

Ruthenium and osmium compounds which are especially preferably used in the process according to the invention are those of one of the formulae XXV to XXVf

(R₉₄R₉₅R₉₆P)L₈Me²⁺(Z¹⁻)₂  (XXV),

(R₉₄R₉₅R₉₆P)₂L₉Me²⁺(Z¹⁻)₂  (XXVa),

(R₉₄R₉₅R₉₆P)L₉L₁₀Me²⁺(Z¹⁻)₂  (XXVb),

(R₉₄R₉₅R₉₆P)₃L₉Me²(Z¹⁻)₂  (XXVc),

 (R₉₄R₉₅R₉₆P)L₉L₉Me²⁺(Z¹⁻)₂  (XXVd),

(R₉₄R₉₅R₉₆P)L₈L₁₀Me²⁺(Z¹⁻)₂  (XXVe),

(R₉₄R₉₅R₉₆P)L₈(L₉)_(m)Me²⁺(Z¹⁻)₂  (XXVf),

in which

Me is Ru or Os;

Z in formulae XXV to XXVe is H⁻, cyclopentadienyl, Cl⁻, Br⁻, BF₄ ⁻, PF₆ ⁻, SbF₆ ⁻, AsF₆ ⁻, CF₃SO₃ ⁻, C₆H₅—SO₃ ⁻, 4-methyl-C₆H₅—SO₃ ⁻, 3,5-dimethyl-C₆H₅—SO₃ ⁻, 2,4,6-trimethyl-C₆H₅—SO₃ ⁻ and 4-CF₃—C₆H₅—SO₃ ⁻ and in formula XXVf is H⁻, cyclopentadienyl, BF₄ ⁻, PF₆ ⁻, SbF₆ ⁻, AsF₆ ⁻, CF₃SO₃ ⁻, C₆H₅—SO₃ ⁻, 4-methyl-C₆H₅—SO₃ ⁻, 2,6-dimethyl-C₆H₅—SO₃ ⁻, 2,4,6-trimethyl-C₆H₅—SO₃ ⁻ or 4-CF₃—C₆H₅—SO₃ ⁻;

R₉₄, R₉₅ and R₉₆ independently of one another are C₁-C₆alkyl, or cyclopentyl or cyclohexyl or cyclopentyloxy or cyclohexyloxy which are unsubstituted or substituted by 1 to 3 C₁-C₄alkyl, or phenyl or benzyl or phenyloxy or benzyloxy which are unsubstituted or substituted by 1 to 3 C₁-C₄alkyl;

L₈ is C₆-C₁₆arene or C₅-C₁₆heteroarene which are unsubstituted or substituted by 1 to 3 C₁-C₄alky, C₁-C₄alkoxy, —OH, —F or Cl;

L₉ is C₁-C₆alkyl-CN, benzonitrile or benzylnitrile; and

L₁₀ is H₂O or C₁-C₆alkanol.

Preferred arenes and heteroarenes are benzene, toluene, xylene, trimethylbenzene, naphthalene, biphenyl, anthracene, acenaphthene, fluorene, phenanthrene, pyrene, chrysene, fluoranthrene, furan, thiophene, pyrrole, pyridine, γ-pyran, γ-thiopyran, pyrimidine, pyrazine, indole, coumarone, thionaphthene, carbazole, dibenzofuran, dibenzothiophene, pyrazole, imidazole, benzimidazole, oxazole, thiazole, isoxazole, isothiazole, quinoline, isoquinoline, acridine, chromene, phenazine, phenoxazine, phenothiazine, triazine, thianthrene and purin. More preferred arenes and heteroarenes are benzene, naphthalene, cumene, thiophene and benzothiophene. The arene is especially preferably benzene or a benzene substituted by C₁-C₄alkyl, for example toluene, xylene, isopropylbenzene, tert-butylbenzene or cumene, and the heteroarene is preferably thiophene.

If the preparation of the ruthenium and osmium catalysts is carried out in solyents which can coordinate to a metal atom, for example alkanols, solvated Ru/Os cation complexes can form, and these are also included in the context of the use of according to the invention.

Some examples of ruthenium and osmium compounds to be used according to the invention are [Tos is tosylate]: (C₆H₁₁)₂HPRu(p-cumene)Cl₂, (C₆H₁₁)₃PRu(p-cumene)Cl₂, (C₆H11 )₃PRu(p-cumene)(Tos)₂, (C₆H₁₁)₃PRu(p-cumene)Br₂, (C₆H₁₁)₃PRu(p-cumene)ClF, (C₆H₁₁)₃PRu(C₆H₆)(Tos)₂, (C₆H₁₁)₃PRu(C₃—C₆H₅)(TOS)₂, (C₆H₁₁)₃PRu(i-C₃H₇—C₆H₅)(Tos)₂, (C₆H₁₁)₃PRu(chrysene)(Tos)₂, (C₆H₁₁)₃PRu(biphenyl)(Tos)₂, (C₆H₁₁)₃PRu(anthracene)(Tos)₂, (C₆H₁₁)₃PRu(C₁₀H₈)(Tos)₂, (i-C₃H₇)₃PRu(p-cumene)Cl₂, (CH₃)₃PRu(p-cumene)Cl₂, (n-C₄H₉)₃PRu(p-cumene)Cl₂, [(C₆H₁₁)₃P]₂Ru(CH₃—CN)(Tos)₂, (C₆H11)₃PRu(CH₃—CN)(C₂H₅—OH)(Tos)₂, (C₆H₁₁)₃PRu(p-cumene)(CH₃—CN)₂(PF₆)₂, (C₆H₁₁)₃PRu(p-cumene)(CH₃—CN)₂(Tos)₂, (n-C₄H₉)₃PRu(p-cumene)(CH₃—CN)₂(Tos)₂, (C₆H₁₁)₃PRu(CH₃CN)Cl₂, (C₆H₁₁)₃PRu(CH₃—CN)₂Cl₂, (C₆H₁₁)₃PRu(p-cumene)(C₂H₅OH)(BF₄)₂, (C₆H₁₁)₃PRu(p-cumene)(C₂H₅OH)₂(BF₄)₂, (C₆H₁₁)₃Pru(p-cumene)(C₂H₅OH)₂(PF₆)₂, (C₆H₁₁)₃PRu(C₆H₆)(C₂H₅OH)₂(Tos)₂, (C₆H₁₁)₃POs(p-cumene)Cl₂, (i-C₃H₇)₃POs(p-cumene)Cl₂, (CH₃)₃POs(p-cumene)Cl₂, (C₆H₅)₃POs(p-cumene)Cl₂, [(C₆H₁₁)₃P]₃Ru(p-cumene)Cl₂ and RuCl₂(p-cumene)[(C₆H₁₁)₂PCH₂CH₂P(C₆H₁₁)₂].

The ruthenium and osmium compounds to be used according to the invention are known or can be prepared by known and analogous processes starting from the metal halides (for example MeX₃ or [MeareneX₂]₂ and reaction with phosphines and ligand-forming agents.

7. Further suitable one-component catalysts are divalently cationic ruthenium or osmium compounds with a metal atom to which 1 to 3 tertiary phosphine ligands with, in the case of ruthenium compounds, sterically bulky substituents, if desired, non-photolabile neutral ligands and anions are bonded for charge balancing, with the proviso that in ruthenium(trisphenylphosphine)dihalides or -hydride-halides the phenyl groups are substituted by C₁-C₁₈alkyl, C₁-C₁₈haloalkyl or C₁-C₁₈alkoxy.

The ruthenium and osmium compounds preferably contain 2 or 3 tertiary phosphine groups. Phosphine groups in the context of the invention are understood as meaning tertiary phophines and phosphites. The number of additional non-photolabile neutral ligands depends on the one hand on the number of phosphine and phosphite ligands, and on the other hand on the valency of the neutral ligands. Monovalent or divalent neutral ligands are preferred.

In a preferred embodiment, the divalently cationic ruthenium and osmium compounds to be used according to the invention contain 3 phosphine or phosphite group s and two monovalent anions for charge balancing; or 3 phosphine or phosphite groups, two monovalent or one divalent non-photolabile neutral ligand, and two monovalent anions for charge balancing; or 2 phosphine or phosphite groups, one monoanionic, additionally monovalent non-photolabile neutral ligands and o one monovalent anion for charge balancing.

The meanings and preferred meanings of non-photolabile ligands (also called highly coordinating ligands) have been mentioned above.

Sterically bulky substituents in the context of the invention are understood as meaning those which shield the ruthenium and osmium atoms sterically. It has thus been found, surprisingly, that linear alkyl groups as substituents in the phosphine and phosphite ligands result in ruthenium compounds without any thermal activity for the metathesis polymerization of strained cycloolefins. It has also been observed that in the case of osmium compounds, surprisingly, linear alkyl groups as substituents in the phosphine and phosphite ligands have an excellent thermocatalytic activity for the metathesis polymerization of strained cycloolefins; however, phosphine and phosphite ligands with sterically bulky substituents are also preferably used for the osmium compounds. It has furthermore been found that the steric shielding of triphenylphosphine ligands in ruthenium dihalides and ruthenium hydride-halides is inadequate, and such catalysts have only a moderate catalytic activity for the metathesis polymerization of strained cycloolefins. The catalytic activity can suprisingly be increased considerably if the tertiary phosphine groups contain phenyl substituted by alkyl or alkoxy groups.

The meanings and preferred meanings of phosphine ligands have been mentioned above. Alkyl R₉₁, R₉₂ and R₉₃ are particularly preferably α-branched alkyl, for example of the formula —CR_(b)R_(c)R_(d), in which R_(b) is H or C₁-C₁₂alkyl, R_(c) is C₁-C₁₂alkyl, and R_(d) is C₁-C₁₂alkyl or phenyl which is unsubstituted or substituted by C₁-C₄alkyl or C₁-C₄alkoxy, and the sum of the C atoms in the radical —CR_(b)R_(c)R_(d) is 3 to 18. Examples of alkyl are i-propyl, i- and t-butyl, 1-methyl- or 1,1-dimethylpropyl-1-yl, 1-methyl- or 1,1-dimethylbut-1-yl, 1-methyl- or 1,1-dimethylpent-1-yl, 1-methyl- or 1,1-dimethylhex-1-yl, 1-methyl- or 1,1-dimethylheptl-1yl [sic], 1-methyl- or 1,1-dimethyloct-1-yl, 1-methyl- or 1,1-dimethylnon-1-yl, 1-methyl- or 1,1-dimethyldec-1-yl, 1-methyl- or 1,1-dimethylundec-1-yl, 1-methyl- or 1,1-dimethyldodec-1-yl, 1-methyl- or 1,1-dimethyltridec-1-yl, 1-methyl- or 1,1-dimethyltetradec-1-yl, 1-methyl- or 1,1-dimethylpentadec-1-yl, 1-methyl- or 1,1-dimethylhexadec-1-yl, 1-methylheptadec-1-yl, phenyl-dimethyl-methyl. Preferred examples are i-propyl, i- and t-butyl.

In the case of the osmium compounds used, R₉₁, R₉₂ and R₉₃can also be linear alkyl having 1 to 18, preferably 1 to 12, more preferably 1 to 8, and particularly preferably 1 to 6 C atoms, for example methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl and n-octyl.

Alkoxy R₉₁, R₉₂ and R₉₃ can contain 3 to 12, more preferably 3 to 8, and particularly preferably 3 to 6 C atoms. The alkoxy is particularly preferably α-branched alkoxy, for example of the formula —OCR_(b)R_(c)R_(d), in which R_(b) is H or C₁-C₁₂alkyl, R_(c) is C₁-C₂alkyl, and R_(d) is C₁-C₁₂alkyl or phenyl which is unsubstituted or substituted by C₁-C₄alkyl or C₁-C₄alkoxy, and the sum of the C atoms in the radical —CR_(b)R_(c)R_(d) is 3 to 18. Examples of alkoxy are i-propyloxy, i- and t-butyloxy, 1-methyl- or 1,1-dimethylprop-1-oxyl, 1-methyl- or 1,1-dimethylbut-1-oxyl, 1-methyl- or 1,1-dimethylpent-1-oxyl, 1-methyl- or 1,1-dimethylhex-1-oxyl, 1-methyl- or 1,1-dimethylhept-1-oxyl, 1-methyl- or 1,1-dimethyloct-1-oxyl, 1-methyl- or 1,1-dimethylnon-1-oxyl, 1-methyl- or 1,1-dimethyldec-1-oxyl, 1-methyl- or 1,1-dimethylundec-1-oxyl, 1-methyl- or 1,1-dimethyldodec-1-oxyl, 1_methyl- or 1,1-dimethyltridec-1-oxyl, 1-methyl- or 1,1-dimethyltetradec-1-oxyl, 1-methyl- or 1,1-dimethylpentadec-1-oxyl, 1-methyl- or 1,1-dimethylhexadec-1-oxyl, 1-methylheptadec-1-oxyl, phenyl-dimethyl-methyl. Preferred examples are i-propyloxy, i- and t-butyloxy.

In the case of the osmium compounds used, R₉₁, R₉₂ and R₉₃ can also be linear alkoxy having 1 to 18, preferably 1 to 12, more preferably 1 to 8, and particularly preferably 1 to 6 C atoms, for example methoxy, ethoxy, n-propyloxy, n-butyloxy, n-pentyloxy, n-hexyloxy, n-heptyloxy and n-octyloxy.

Cycloalkyl R₉₁, R₉₂ and R₉₃ are preferably C₁-C₈cycloalkyl, and particularly preferably C₅- or C₆cycloalkyl. Some examples are cyclobutyl, cycloheptyl, cyclooctyl and in particular, cyclopentyl and cyclohexyl, which are preferably unsubstituted or substituted by 1 to 3 alkyl, haloalkyl or alkoxy groups.

Cycloalkyloxy R₉₁, R₉₂ and R₉₃ are preferably C₅-C₈cycloalkyloxy, and particularly preferably C₅- or C₆cycloalkyloxy. Some examples are cyclobutyloxy, cycloheptyloxy, cyclooctyloxy and, in particular, cyclopentyloxy and cyclohexyloxy, which are preferably unsubstituted or substituted by 1 to 3 alkyl, haloalkyl or alkoxy groups.

In a preferred embodiment, the phosphine ligands are those of the formula XXIII in which R₉₁, R₉₂ and R₉₃ independently of one another are α-branched C₃-C₈alkyl, cyclopentyl or cyclohexyl which are unsubstituted or substituted by C₁-C₄alkyl, or phenyl which is unsubstituted or substituted by C₁-C₄alkyl, C₁-C₄alkyl [sic] C₁-C₄alkoxy or trifluoromethyl. Particularly preferred examples of phosphine ligands of the formula XXIII are (C₆H₅)₃P, (C₅H₉)₃P, (C₆H₁₁)₃P, (i-C₃H₇)₃P, (i-C₄H₉)₃P, (t-C₄H₉)₃P, [C₂H₅—CH(CH₃)]₃P, [C₂H₅—C(CH₃)₂]₃P, (2-methylphenyl)₃P, (2,3-dimethylphenyl)₃P, (2,4-dimethylphenyl)₃P, (2,6-dimethylphenyl)₃P, (2-methyl-4-i-propylphenyl)₃P, (2-methyl-3-i-propylphenyl)₃P, (2-methyl-5-i-propylphenyl)₃P, (2,4-di-t-butylphenyl)₃P, (2-methyl-6-i-propylphenyl)₃P, (2-methyl-3-t-butylphenyl)₃P, (2,5-di-t-butylphenyl)₃P, (2-methyl4-t-butylphenyl)₃P, (2-methyl-5-i-butylphenyl)₃P, (2,3-di-t-butylphenyl)₃P and (2,6-di-t-butylphenyl)₃P.

In another preferred embodiment, the phosphite ligands are those of the formula XXIII in which R₉₁, R₉₂ and R₉₃ independently of one another are α-branched C₃-C₈alkoxy, or cyclopentyloxy or cyclohexyloxy which are unsubstituted or substituted by C₁-C₄alkyl; or phenyloxy which is unsubstituted or substituted by C₁-C₄alkyl, C₁-C₄alkoxy or trifluoromethyl. Examples of phosphites have been mentioned above.

Examples and preferred meanings of suitable anions have been mentioned above.

In a preferred embodiment, the ruthenium and osmium compounds are particularly preferably those of the formulae XXVI, XXVIa, XXVIb, XXVIc or XXVId

Me²⁺(L₁₁)₂(L₁₂)(Y₁ ⁻)₂  (XXVI),

Me²⁺(L₁₁)₃(Y₁ ⁻)₂  (XXVIa),

Me²⁺(L₁₁)₂L₁₃(Y₁ ⁻)  (XXVIb),

Me²⁺(L₁₁)₃L₁₄(Y₁ ⁻)₂  (XXVIc),

Me²⁺L₁₁(L₁₂)₃(Y₁ ⁻)₂  (XXVId),

in which

Me is Ru or Os;

Y₁ is the anion of a monobasic acid;

L₁₁ is a phosphine of the formula XXIII or XXIIIa;

L₁₂ is a neutral ligand;

L₁₃ is cyclopentadienyl which is unsubstituted or substituted by C₁-C₄alkyl; and

L₁₄ is CO.

For the individual meanings of L₁₁, L₁₂, L₁₃ and Y₁, the above preferred meanings apply.

In a particularly preferred embodiment, in formula XXVI L₁₂ is a C₁-C₄alkanol, in formula XXVIb, Y₁ is Cl or Br, in formula XXVIc Y₁ is H, and in the formulae XXVI to XXVIc L₁₁ is tri-i-propylphosphine, tricyclohexylphosphine, triphenylphosphine or triphenyiphosphine which is substituted by 1 to 3 C₁-C₄alkyl in the phenyl groups.

Some examples of ruthenium and osmium compounds to be used according to the invention are [(C₆H₁₁)₃P]₂Ru(CH₃OH)₂(ToS)₂, [(C₆H₁₁)₃P]₂RuCl₂ and [(C₆H₁₁)₃P]₃Ru(CH₃OH)₂.

The ruthenium and osmium compounds to be used according to the invention are known or can be prepared by known and analogous processes starting from the metal halides (for example MeX₃, [Me(diolefin)X₂]₂ or [Me-areneX₂]₂ and reaction with phosphines and ligand-forming agents.

The compositions according to the invention are surprisingly stable to storage and can be marketed as such. However, it is also possible to mix the individual components together before processing. If air- and/or moisture-sensitive catalysts are used, storage with exclusion of air and moisture is advisable. Since the novel crosslinking principle is not based on a free radical, anionic or cationic reaction, practically no interruption or slowing of the reaction is observed on carrying out the polymerization in air, which offers considerable advantages during processing, for example no extensive protective precautions. The possibility of using solyent-free systems in the case of liquid polymers of low molecular weight or in the case of solutions with reactive strained cycloolefins which are capable of metathesis polymerization as comonomers is a great surprising advantage.

The invention also relates to a process for the preparation of crosslinked polymers by metathesis polymerization, wherein a composition of

(a) a catalytic amount of a one-component catalyst for metathesis polymerization and

(b) at least one polymer with strained cycloalkenylene radicals bonded in the polymer backbone, alone or mixed with strained cycloolefins,

(c) is polymerized by heating,

(d) is polymerized by irradiation,

(e) is polymerized by heating and irradiation,

(f) the one-component catalyst is activated by brief heating and the polymerization is brought to completion by irradiation, or

(g) the one-component catalyst is activated by brief irradiation and the polymerization is brought to completion by heating.

Heating can mean a temperature of 50 to 300° C., preferably 60 to 250° C., particularly preferably 60 to 200° C., and especially preferably 60 to 150° C. The polymerization times essentially depend on the catalyst activity, and the times can extend from several seconds to minutes and hours.

In the process according to the invention, it is not necessary to maintain the irradiation of the reaction mixture over the entire duration of the reaction. Once the polymerization has been initiated photochemically, the subsequent course of the reaction takes place independently, even in the dark. Irradiation is advantageously carried out with light of a wavelength in the range from 50 nm to 1000 nm, preferably in the range from 200 nm to 500 nm and especially preferably in the UV range. The irradiation time depends on the nature of the light source. Suitable sources of irradiation are, for example, the sun, sources of laser radiation, X-ray radiation and, in particular, sources of UV radiation. UV lasers or UV lamps are preferably employed according to the invention. The irradiation of the catalyst can be carried out both before, during and after the addition of the monomer.

Suitable irradiation times are from one second to several hours, in particular minutes to hours. The sequence of the addition of monomers and catalysts is not critical. The monomer can be both initially introduced into the reaction vessel and added after introduction of the catalyst. Likewise, the catalyst can be pre-irradiated and then added to the monomer. It is furthermore also possible to irradiate the solution comprising catalyst and monomer.

In the case of irradiation using photoactive catalysts, the process according to the invention is preferably carried out at room temperature to slightly elevated temperature. An increase in temperature in this case essentially serves to increase the rate of reaction. At the temperatures chosen to accelerate the reaction, a photopolymerization therefore also chiefly takes place. However, it should be mentioned that the catalysts can be converted into thermoactive catalysts by adequate irradiation or elevated temperature. It is furthermore to be noted that some catalysts are capable of initiating the metathesis polymerization both thermally and [lacuna] irradiation.

In particular, the process according to the invention is carried out with irradiation preferably at temperatures of −20 to +110° C., particularly preferably 20 to 80° C.

The irradiation time essentially depends on the desired reaction procedure. Brief irradiation is chosen, for example, if the polymerization is only to be initiated by irradiation and is to be brought to completion by heating. This can mean an irradiation time of up to 60 seconds, preferably 5 to 60 seconds, and particularly preferably 10 to 40 seconds. A longer irradiation time is chosen, for example, if the polymerization is to be carried out chiefly with irradiation and the final polymerization is to be brought to completion only by after-heating.

A quite particular and surprising advantage of the process according to the invention is that one-component catalysts used act as thermal catalysts after the irradiation. This results in the possibility of continuing the polymerization and bringing it to completion by supplying heat after a short irradiation time, which offers economic and industrial advantages in various areas of production of shaped articles or coatings.

The present invention also relates to crosslinked metathesis polymers of a polymer with strained cycloalkenylene radicals bonded in the polymer backbone, alone or as a mixture with strained cycloolefins.

The present invention also relates to metathesis polymers, crosslinked using a one-component catalyst, from a composition comprising

(a) a catalytic amount of a one-component catalyst for the metathesis polymerization and

(b) at least one polymer with strained cycloalkenylene radicals bonded in the polymer backbone, alone or as a mixture with strained cycloolefins.

Materials for production of shaped articles by machining, or shaped articles of all types directly, as well as coatings and relief images can be produced with the process according to the invention. The invention also relates to shaped articles of crosslinked metathesis polymers of the composition according to the invention.

The polymers according to the invention can have very different properties, depending on the monomer used. Some are distinguished by a very high permeability to oxygen, low dielectric constants, good heat stability and low absorption of water. Others have outstanding optical properties, for example high transparency and low refractive indices. Furthermore, the low shrinkage is to be singled out in particular. They can therefore be used in very different industrial fields.

As layers on the surfaces of carrier materials, the compositions according to the invention are distinguished by a high adhesive strength. The coated materials are furthermore distinguished by a high surface smoothness and gloss. Among the good mechanical properties, the low shrinkage and the high impact strength are to be singled out in particular, and also the heat stability. The ease of removal from the moulds during processing in moulds and the high resistance to solyents are furthermore to be mentioned.

These polymers are suitable for the production of medical equipment, implants or contact lenses; for the production of electronic components; as binders for coatings; as photocurable compositions for model construction or as adhesives for gluing substrates of low surface energy (for example Teflon, polyethylene and polypropylene, silicone rubber), and as photopolymerizable compositions in stereolithography. The compositions according to the invention can also be used for the production of coatings by photopolymerization, it being possible for on the one hand clear (transparent) and even pigmented compositions to be used. Both white and coloured pigments can be used.

The photocurable compositions according to the invention are particularly suitable for the production of protective coatings and relief images. The invention also relates to a variant of the process according to the invention for the production of coated materials or relief images on carrier materials, in which a composition according to the invention and, if desired, a solyent are applied as a layer to a carrier, for example by dipping, brushing, pouring, rolling, knife-coating or whirler coating processes, the solyent is removed, if desired, and the layer is irradiated or heated for polymerization, or the layer is irradiated through a photomask and the non-irradiated portions are then removed with a solyent. This can then also be followed by heat treatment. Using this process, surfaces of substrates can be modified or protected, or, for example, printed circuits, printing plates or printing rolls can be produced. In the production of printed circuits, the compositions according to the invention can also be employed as solder resists. Other possible uses are the production of screen printing masks and the use as radiation-curable printing inks for offset, screen and flexographic printing. Because of the high adhesion and the low absorption of water, the protective coatings on carrier materials are especially suitable for corrosion protection.

The present invention furthermore relates to a coated carrier material, wherein a layer of a composition according to the invention is applied to a substrate.

The present invention also relates to a coated substrate with a cured layer of a composition according to the invention. The exceptionally high adhesive strength of the layers, even on metal surfaces, is to be singled out in particular, even when the products are pure hydrocarbon polymers.

Suitable substrates (carrier materials) are, for example, those of glass, minerals, ceramics, plastics, wood, semimetals, metals, metal oxides and metal nitrides. The layer thicknesses essentially depend on the desired use, and can be, for example, 0.1 to 1000 μm, preferably 0.5 to 500 μm, particularly preferably 1 to 100 μm. The coated materials are distinguished by a high adhesive strength and good thermal and mechanical properties.

The coated materials according to the invention can be prepared by known methods, for example brushing, knife-coating or casting processes, such as curtain pouring or spin coating.

The compositions according to the invention can also be used as adhesives which cure by means of heat or by means of radiation, for firmly bonding the most diverse materials, it being possible for outstanding peel strengths to be achieved.

In addition to the high adhesive strengths, the outstanding processability, the good surface properties (smoothness, gloss), the high crosslinking density and the resistance to solvents and other liquids, the polymers according to the invention are also distinguished in particular by very good physico-mechanical properties, for example high heat resistance, breaking and flexural strength and impact strength, and outstanding electrical properties, for example low surface tensions and charges (very low ε and tan δ values). The high permeability to oxygen and the low absorption of water are furthermore to be mentioned. Polymers built up only from carbon and hydrogen are particularly valuable ecologically, since, for example, they can be incinerated by pyrrolysis [sic] or without the formation of harmful by-products. Because of their outstanding electrical properties, these polymers are particularly suitable for applications in the field of electrical engineering and electronics, in particular as insulating materials (for example coil encapsulation).

The following examples illustrate the invention in more detail.

A) Preparation of Polymers with Strained Cycloolefin Rings in the Polymer Backbone

EXAMPLE A1

Preparation of

55.1 g (0.5 mol) of Vestenamer® 6213 (cyclooctene polymerized by metathesis, Hüls AG) are dissolved in 200 ml of toluene, the solution is mixed with 33.05 g (0.25 mol) of dicyclopentadiene and the mixture is heated at 190° C. in an autoclave for 8 hours. During this operation, the dicyclopentadiene is cleaved to give cyclopentadiene, which reacts with the Vestenamer to form norbornene groups. The reaction mixture is then poured into methanol/acetone (1:1), while stirring, and the polymer which has precipitated out is filtered off and then dried. Yield 50.4 g (76%). Elemental analysis, % calculated (found): C 88.57 (88.38), H 11.43 (11.60).

¹H-NMR analysis shows that 35% of the double bonds of the Vestenamer have been converted into norbornene units (x=0.35 and y=0.65). M_(n)=8500 g/mol; M_(w)=170,000 g/mol, determined by gel permeation chromatography in tetrahydrofuran with polystyrene standards.

EXAMPLE A2

Preparation of

55.1 g (0.5 mol) of Vestenamer® L3000 (cyclooctene of low molecular weight polymerized by metathesis, Hüls AG, Marl) are mixed with 33.5 g (0.25 mol) of dicyclopentadiene without a solvent and the mixture is heated at 190° C. in an autoclave for 8 hours. Working up and analysis of the reaction mixture are carried out analogously to Example A1. Yield 47.5 g (77%). Elemental analysis, % calculated (found): C, 88.57 (88.54), H, 11.43 (11.32). ¹H-NMR analysis shows that 28% of the double bonds of the Vestenamer have been converted into norbornene units (x=0.28 and y=0.72). M_(n)=500 g/mol; M_(w)=5000 g/mol.

EXAMPLE A3

Preparation of Linear Polydicyclopentadiene with Structural Elements

0.25 g of [W(N—C₆H₅)(CH₂Si(CH₃)₃)₂(OC(CH₃)₃)Cl] is dissolved in 150 of toluene, and 30 ml of dicyclopentadiene are added. Irradiation is carried out for 30 minutes with a 1000W Xenon lamp with an IR water filter from a distance of one meter. Thereafter, 1 ml of benzaldehyde is added and the mixture is stirred at room temperature for a further hour. It is added dropwise to 1.51 of methanol and the polymer which has precipitated out is filtered off and dried in vacuo at room temperature. The yield of crude product is 22.6 g. 200 ml of toluene are added to the crude product and the mixture is stirred at room temperature for 3 days. It is centrifuged and the toluene solution is decanted off, and subsequently stirred into 1.51 of methanol. The white polymer which has precipitated out is filtered off and dried in vacuo. The yield of polymer is 5.62 g (19%). The polymer is very readily soluble in toluene.

EXAMPLE A4

Preparation of

(a) 15.0 g (0.091 mol) of norbornene-1,2-dicarboxylic anhydride are dissolved in 200 ml of toluene at 80° C. A solution of 5.29 g (0.0455 mol) of 1,6-diaminohexane in 50 ml of toluene is added dropwise with stirring. After 30 minutes at 80° C. the mixture is cooled and filtered. The residue is powdered and dried under a high vacuum at 40° C. for 24 h. Yield: 16.5 g (81.6%). Melting point: 164° C.; IR (KBr): ν(C═O): 1635 cm⁻¹ (amide) and 1695 cm⁻¹ (carboxylic acid); ¹H-NMR (DMSO-d₆): inter alia 5.92-6.16 ppm: 4 olefin-H of the norbornene units; elemental analysis (C₂₄H₃₂N₂O₆): calculated: C, 64.85; H, 7.26; N, 6.30; found: C, 66.64, H, 8.34; N, 7.22.

(b) 1.0 g (11 mmol) of 1,4-butanediol and 7.84 g (11 mmol) of the product obtained in (a) are dissolved in 50 ml of dimethylformamide. 4.54 g (22 mmol) of dicyclohexylcarbodiimide are added in portions with stirring and under an N₂ atmosphere, and the mixture is heated at 50° C. for 14 h. After cooling, the mixture is filtered and the filtrate is precipitated in 1 l of water. Filtration and drying give the title compound. Yield: 4.2 g (84%); GPC (THF, PS standards): M_(n)=5100 g/mol; M_(w)=13,000 g/mol; elemental analysis (C₂₈H₃₈N₂O₆)_(n): calculated: C, 67.44; H, 7.68; N, 5.62; found: C, 66.88, H, 7.70; N, 5.87; soluble in DMSO, DMF, CHCl₃, THF, dioxane

EXAMPLE A5

Preparation of

(a) 15.0 g (0.090 mol) of 7-oxanorbornene-1,2-dicarboxylic anhydride are dissolved in 135 ml of dioxane at 60° C. A solution of 5.23 g (0.045 mol) of 1,6-diaminohexane in 50 ml of toluene is added dropwise with stirring. After 30 minutes at 60° C. the mixture is cooled and filtered. The residue is powdered and dried under a high vacuum at 40° C. for 24 h. Yield: 13.09 g (64.9%). Melting point: 120° C. (decomposes); IR (KBr): ν(C═O): 1632 cm⁻¹ (amide) and 1700 cm⁻¹ (carboxylic acid); ¹H-NMR (DMSO-d₆): inter alia 6.0-6.5 ppm: 4 olefin-H of the 7-oxanorbornene units; elemental analysis (C₂₂H₂₈N₂O₈): calculated: C, 64.85; H, 7.26; N, 6.30; found: C, 66.64, H, 8.34; N, 7.22.

(b) 1.0 g (11 mmol) of 1,4-butanediol and 5.0 g (11 mmol) of the product obtained in (a) are dissolved in 50 ml of dimethylformamide. 4.54 g (22 mmol) of dicyclohexylcarbodiimide are added in portions with stirring and under an N₂ atmosphere, and the mixture is heated at 50° C. for 14 h. After cooling, the mixture is filtered and the filtrate is concentrated in a rotary evaporator. Drying gives the title compound. Yield: 5.2 g (94%); GPC (THF, PS standards): M_(n)=7400 g/mol; M_(w)=20,800 g/mol; elemental analysis (C₂₆H₃₄N₂O₈)_(n): calculated: C, 62.14; H, 6.82; N, 5.57; found: C, 61.74, H, 7.12; N, 6.01; soluble in DMSO, DMF, CHCl₃, THF, dioxane

B) Use Examples

EXAMPLE B1

Thermal Polymerization

In 1 ml of a 20% solution of the polymer according to Example A1 in chloroform, (a) 5 mg of Ru[p-cumene][P(C₆H,₁₁)₃]₃Cl₂ or (b) 5 mg of Ru[P(C₆H₁₁) ₃]₃(CH₃OH)₂ are dissolved. The mixtures are cast to films on glass plates with a doctor blade of 100 μm slit width. The solvent is evaporated off at room temperature for 1 hour and the film is then dried at 50° C. in vacuo for 1 hour. The coated plates are stable to storage. The layers can be detached with toluene. The coated glass plates are heated either at 65° C. for 4 hours or at 80° C. for 2 hours. After cooling, the plates are placed in water, whereupon a transparent, practically colourless and unsupported film can be detached from the glass plate. The crosslinking is demonstrated by the insolubility and swellability of the film in toluene. The films have an elasticity modulus of 2 MPa (Minimat tensile tester). Dielectric constants (ε) and and [sic] loss factors (tan δ) at 30° C. and various frequencies (ν):

ν ε tan δ (%) 200 Hz 2.8 <0.01 1000 Hz 2.7 0.01 10,000 Hz 2.7 0.015 100 kHz 2.6 0.025 1 MHz 2.5 0.03 10 MHz 2.4 0.05 100 MHz 2.3 0.05 1 GHz 2.2 not determined

EXAMPLE B2

Thermal Polymerization

Analogously to Example B1, 5 mg of Ru[p-cumene][P(C₆H₁₁)₃]₃Cl₂, as the catalyst, are dissolved in 1 g of the polymer according to Example A2 by heating to 60° C. and the solvent-free mixture is applied hot to a heated glass plate with a doctor blade. The coated plate is heated at 80° C. for 2 hours. After cooling, a pale yellow transparent and unsupported film is detached from the glass plate. The film is insoluble in toluene.

EXAMPLE B3

Thermal Polymerization

Analogously to Example B1, a 5% solution of the polymer according to Example A3 is dissolved in toluene with 0.5% by weight of Ru[p-cumene][P(C₆H₁₁)₃]₃Cl₂ as the catalyst, and the mixture is applied to a heated glass plate with a layer thickness of 20 μm using a doctor blade. The coated plate is heated at 80° C. for 2 hours. After cooling, a transparent and unsupported film which swells only very slightly in toluene is detached from the glass plate.

EXAMPLE B4

Thermal Polymerization

The procedure is analogous to Example 3 and a film is formed on a copper foil. After the polymerization, the film has excellent adhesion to the copper foil. The coated copper foil is steeped in water for one week; even after this, the film cannot be detached from the copper film.

EXAMPLE A5

Photopolymerization

A layer about 1 μm thick is applied to an Si semiconductor plate (wafer) by means of spin coating with a 10% solution of the polymer according to Example A1 and and [sic] 1% by weight (based on the polymer) of Ta[CH₂—Si(CH₃)₃]₃Cl₂, as the catalyst, in toluene. The layer is exposed to an Oriel 350W UV lamp under a mask for 15 seconds, subsequently heated at 80° C. for 30 seconds and then developed with methylene chloride. A relief image with a resolution of about 1 μm is obtained.

EXAMPLE B6

Photopolymerization

The solution used according to Example B5 is applied to a copper-coated epoxy laminate (printed circuit board) with a layer thickness of 50 μm using a doctor blade (slit width 500 μm). The layer is then heated at 70° C. for 1 minute and subsequently exposed to a Höhnle 3000W UV lamp under a printed circuit board mask for 3 minutes. It is then heated at 70° C. for 3 minutes and subsequently developed with methylene chloride. A negative relief image of high resolution is obtained.

EXAMPLE B7

Photopolymerization

A layer about 1 μm thick is applied to an Si semiconductor plate (wafer) by means of spin coating with a 10% solution of the polymer according to Example A3 and and [sic] 2% by weight (based on the polymer) of Ta[CH₂—Si(CH₃)₃]₃Cl₂, as the catalyst, in toluene. The layer is exposed to an Oriel 350W UV lamp under a resist mask for 5 seconds, subsequently heated at 80° C. for 30 seconds and then developed with toluene. A relief image with a resolution of about 0.7 μm is obtained.

EXAMPLE B8

Photopolymerization

A layer about 1 μm thick is applied to an Si semiconductor plate (wafer) by means of spin coating with a 10% solution of the polymer according to Example A4 and and [sic] 1% by weight (based on the polymer) of Ta[CH₂—Si(CH₃)₃]₃Cl₂in dioxane. The layer is exposed to an Oriel 350W UV lamp under a resist mask for 100 seconds and then developed with dioxane. A relief image with a high resolution is obtained.

EXAMPLE B9

Photopolymerization

A layer about 1 μm thick is applied to an Si semiconductor plate (wafer) by means of spin coating with a 10% solution of the polymer according to Example A5 and and [sic] 1% by weight (based on the polymer) of Ta[CH₂—Si(CH₃)₃]₃Cl₂ in dioxane.

The layer is exposed to an Oriel 350W UV lamp under a resist mask for 100 seconds and then developed with dioxane. A relief image with a high resolution is obtained.

EXAMPLE B10

Photocrosslinking

0.5 g of the polymer according to Example A4 are dissolved in 5 ml of dioxane together with 5 mg of [Ru(C₆H₆)₂](Tos)₂. The solution is poured onto a glass plate and a film about 30 μm thick is produced by means of a doctor blade. Exposure is carried out for 3 minutes under a UV lamp, after which the clear, transparent films can no longer be dissolved, in particular neither in DMSO nor in dioxane.

EXAMPLE B11

Photocrosslinking

0.5 g of the polymer according to Example A4 are dissolved in 5 ml of dioxane together with 5 mg of [Ru(CH₃CN)₆](Tos)₂. The solution is poured onto a glass plate and a film about 30 μm thick is produced by means of a doctor blade. Exposure is carried out for 3 minutes under a UV lamp, after which the clear, transparent films can no longer be dissolved, in particular neither in DMSO nor in dioxane.

EXAMPLE B12

Photocrosslinking

0.5 g of the polymer according to Example A4 are dissolved in 5 ml of dioxane together with 5 mg of [Ru(CH₃CH₂CN)₆](Tos)₂. The solution is poured onto a glass plate and a film about 30 μm thick is produced by means of a doctor blade. Exposure is carried out for 3 minutes under a UV lamp, after which the clear, transparent films can no longer be dissolved, in particular neither in DMSO nor in dioxane.

EXAMPLE B13

Photocrosslinking

0.5 g of the polymer according to Example A5 are dissolved in 5 ml of dioxane together with 5 mg of [Ru(C₆H₆)₂](Tos)₂. The solution is poured onto a glass plate and a film about 30 μm thick is produced by means of a doctor blade. Exposure is carried out for 3 minutes under a UV lamp, after which the clear, transparent films can no longer be dissolved, in particular neither in DMSO nor in dioxane.

EXAMPLE B14

Photocrosslinking

0.5 g of the polymer according to Example A5 are dissolved in 5 ml of dioxane together with 5 mg of [Ru(CH₃CN)₆](Tos)₂. The solution is poured onto a glass plate and a film about 30 μum thick is produced by means of a doctor blade. Exposure is carried out for 3 minutes under a UV lamp, after which the clear, transparent films can no longer be dissolved, in particular neither in DMSO nor in dioxane.

EXAMPLE B15

Photocrosslinking

0.5 g of the polymer according to Example A5 are dissolved in 5 ml of dioxane together with 5 mg of [Ru(CH₃CH₂CN)₆](Tos)₂. The solution is poured onto a glass plate and a film about 30 μm thick is produced by means of a doctor blade. Exposure is carried out for 3 minutes under a UV lamp, after which the clear, transparent films can no longer be dissolved, in particular neither in DMSO nor in dioxane.

EXAMPLE B16

Thermal Crosslinking

A film about 50 μm thick is produced on a glass plate by means of a doctor blade from a 10% solution of the polymer according to Example A4 in dioxane together with 1% (based on the polymer) of RuCl₂(p-cumene)P(C₆H₁₁)₃ and subsequent evaporation of the solvent at 80° C. The film is crosslinked by heating at 120° C. for 1 h. After detaching it from the glass plate, a tear-resistant film is obtained which is insoluble in both dioxane and DMF.

EXAMPLE B17

Thermal Crosslinking

A film about 50 μm thick is produced on a glass plate by means of a doctor blade from a 10% solution of the polymer according to Example A5 in dioxane together with 1% (based on the polymer) of RuCl₂(p-cumene)P(C₆H₁₁)₃ and subsequent evaporation of the solvent at 80° C. The film is crosslinked by heating at 120° C. for 1 h. After detaching it from the glass plate, a tear-resistant film is obtained which is insoluble in both dioxane and DMF.

EXAMPLE B18

Thermal Crosslinking

A layer 500 μm thick of a 10% solution of the polymer according to Example A1 and 1% of [(C₆H₁₁)₃P]₂Ru(CH₃OH)₂(Tos)₂ in toluene is applied to an iron panel.

Following the evaporation of the toluene, the polymer is crosslinked at 80° C. for 1 h. The resulting film is insoluble in CH₂Cl₂.

EXAMPLE B19

Thermal Crosslinking

A layer 500 μm thick of a 10% solution of the polymer according to Example A1 and 1% of [(C₆H₁₁)₃P]₂RuCl₂ in toluene is applied to an iron panel. Following the evaporation of the toluene, the polymer is crosslinked at 80° C. for 1 h. The resulting film is insoluble in CH₂Cl₂. 

What is claimed is:
 1. A composition comprising (a) a catalytic amount of a one-component catalyst for metathesis polymerization, which one-component catalyst is selected from the group consisting of ruthenium and osmium compounds of the formulas XXV to XXVf (R₉₄R₉₅R₉₆P)L₈Me²⁺(Z¹⁻)₂  (XXV) (R₉₄R₉₅R₉₆P)₂L₉Me²⁺(Z¹⁻⁾ ₂  (XXVa) (R₉₄R₉₅R₉₆P)L₉L₁₀Me²⁺(Z¹⁻)₂  (XXVb) (R₉₄R₉₅R₉₆P)₃L₉Me²⁺(Z¹⁻)₂  (XXVc) (R₉₄R₉₅R₉₆P)L₉L₉Me²⁺(Z¹⁻)₂  (XXVd) (R₉₄R₉₅R₉₆P)L₈L₁₀Me²⁺(Z¹⁻)₂  (XXVe) (R₉₄R₉₅R₉₆P)L₈(L₉)_(m)Me²⁺(Z¹⁻)₂  (XXVf)  wherein Me is Ru or Os; Z in formulas XXV to XXVe is H⁻, cyclopentadienyl, Cl⁻, Br⁻, BF₄ ⁻, PF₆ ⁻, SbF₆ ⁻, AsF₆ ⁻, CF₃SO₃ ⁻, C₆H₅—SO₃ ⁻, 4-methyl-C₆H₄—SO₃ ⁻, 3,5-dimethyl-C₆H₃—SO₃ ⁻, 2,4,6-trimethyl-C₆H₂—SO₃ ⁻ and 4—CF₃—C₆H₄—SO₃—; or Z in formula XXVf is H⁻, cyclopentadienyl, BF₄ ⁻, PF₆ ⁻, SbF₆ ⁻, AsF₆ ⁻, CF₃SO₃ ⁻, C₆H₅—SO₃ ⁻, 4-methyl-C₆H₄—SO₃ ⁻, 3,5-dimethyl-C₆H₃—SO₃ ⁻, 2,4,6-trimethyl-C₆H₂—SO₃ ⁻ and 4-CF₃—C₆H₄—SO₃—; or R₉₄, R₉₅ and R₉₆ independently of one another are C₁-C₆alkyl, or cyclopentyl or cyclohexyl or cyclopentyloxy or cyclohexyloxy which are unsubstituted or substituted by one to three C₁-C₄alkyl, or phenyl or benzyl or phenoxy or benzyloxy which are unsubstituted by one to three C₁-C₄alkyl; L₈ is C₆-C₁₆arene or C₅-C₁₆heteroarene which are unsubstituted or substituted by one to three C₁-C₄alkyl, C₁-C₄alkoxy, —OH, —F or —Cl; L₉ is C₁-C₆alkyl-CN, benzonitrile or benzylnitrile; and L₁₀ is H₂O or C₁-C₆alkanol; and (b) at least one polymer with strained cycloalkenylene radicals bonded in the polymer backbone, alone or mixed with a strained cycloolefin.
 2. A composition according to claim 1, wherein the polymers are those with recurring structural units of the formula (a) in the polymer backbone

in which R₀₁ and R₀₂ independently of one another are H or C₁-C₆alkyl, or R₀₁ and R₀₂ together are a bond, and A, together with the C—C group, forms an unsubstituted or substituted strained cycloolefin ring.
 3. A composition according to claim 2, wherein the structural units of the formula (a) are bonded directly or via bridge groups.
 4. A composition according to claim 2, wherein R₀₁ and R₀₂ are H.
 5. A composition according to claim 2, wherein in formula (a) R₀₁ and R₀₂ together are a bond, and A is unsubstituted or substituted C₁-C₁₂alkylene, unsubstituted or substituted C₂-C₁₂heteroalkylene, with at least one heteroatom from the group consisting of O, S and N; unsubstituted or substituted C₅-C₁₂cycloalkylene, unsubstituted or substituted C₄-C₁₂heterocycloalkylene, with at least one heteroatom from the group consisting of O, S and N; unsubstituted or substituted C₂-C₁₂alkenylene; unsubstituted or substituted C₃-C₁₂heteroalkenylene, with at least one heteroatom from the group consisting of O, S and N; unsubstituted or substituted C₅-C₁₂cycloalkenylene; or unsubstituted or substituted C₄-C₁₂heterocycloalkenylene, with at least one heteroatom from the group consisting of O, S and N; or R₀₁ and R₀₂ independently of one another are H or C₁-C₆alkyl and A is unsubstituted or substituted C₅-C₁₂-cycloalkenylene; unsubstituted or substituted C₄-C₁₂heterocycloalkenylene, with at least one heteroatom from the group consisting of O, S and N; or unsubstituted or substituted C₅-C₁₂cycloalkdienylene; or R₀₁ are a double bond together with a terminal C atom of the radical A; R₀₂ is H or C₁-C₆alkyl; and A unsubstituted or substituted C₁-C₁₂alkylene, unsubstituted or substituted C₃-C₁₂heteroalkylene, with at least one heteroatom from the group consisting of O, S and N; unsubstituted or substituted C₅-C₁₂cycloalkylene; unsubstituted or substituted C₄-C₁₂heterocycloalkylene with at least one heteroatom from the group consisting of O, S and N; unsubstituted or substituted C₂-C₁₂alkenylene; unsubstituted or substituted C₃-C₁₂heteroalkenylene with at least one heteroatom from the group consisting of O, S and N; unsubstituted or substituted C₅-C₁₂cycloalkenylene; or unsubstituted or substituted C₄-C₁₂heterocycloalkenylene with at least one heteroatom from the group consisting of O, S and N; or R₀₁ and R₀₂ each are a double bond together with in each case a terminal C atom of the radical A, and A is unsubstituted or substituted C₃-C₁₂alkylene; unsubstituted or substituted C₃-C₁₂heteroalkylene, with at least one heteroatom from the group consisting of O, S and N; unsubstituted or substituted C₅-C₁₂cycloalkylene; or unsubstituted or substituted C₄-C₁₂heterocycloalkylene, with at least one heteroatom from the group consisting of O, S and N; it being possible for phenylene, C₄-C₈cycloalkylene or C₄-C₈heterocycloalkylene to be fused onto the alkylene, heteroalkylene, cycloalkylene, heterocycloalkylene, alkenylene, heteroalkenylene, cycloalkenylene, heterocycloalkenylene, alkdienylene, heteroalkdienylene, cycloalkdienylene and heterocycloalkdienylene.
 6. A composition according to claim 5, wherein R₀₁ and R₀₂ together are a bond, and A is unsubstituted or substituted C₂-C₆alkylene, unsubstituted or substituted C₃-C₇cycloalkylene, unsubstituted or substituted C₂-C₆alkenylene or unsubstituted or substituted C₅-C₇cycloalkenylene; or R₀₁ and R₀₂ independently of one another are H or C₁-C₄alkyl and A is unsubstituted or substituted C₅-C₇cycloalkenylene; or R₀₁ is a double bond together with a terminal C atom of the radical A; R₀₂ is H or C₁-C₄alkyl; and A is unsubstituted or substituted C₂-C₆alkenylene, unsubstituted or substituted C₅-C₇cycloalkylene, unsubstituted or substituted C₂-C₆alkenylene or unsubstituted or substituted C₅-C₇cycloalkenylene; or R₀₁ and R₀₂ each are a double bond together with in each case a terminal C atom of the radical A and A is unsubstituted or substituted C₃-C₆alkylene or unsubstituted or substituted C₅-C₇cycloalkylene.
 7. A composition according to claim 1, wherein the polymers are homo- or copolymers.
 8. A composition according to claim 2, wherein the polymer contains the structural elements of the formula (a) to the extent of at least 5 mol %, based on the polymer.
 9. A composition according to claim 8, wherein the polymer contains the structural elements of the formula (a) to the extent of 5 to 100 mol %.
 10. A composition according to claim 1, wherein the polymers with a carbon backbone are metathesis polymers or copolymers of strained cycloolefins with a double bond in the ring and olefinically unsaturated comonomers, of which the olefinic double bonds in the polymer backbone are reacted partly or completely with open-chain or cyclic 1,3-dienes having 4 to 12 C atoms in a Diels-Alder reaction to give cycloalkenylene radicals having 6 to 14 C atoms.
 11. A composition according to claim 10, wherein 5 to 80% of the double bonds are reacted.
 12. A composition according to claim 10, wherein the metathesis polymers contain recurring structural elements of the formula (t)

in which A, is mono- or bicyclic C₅-C₈cycloalkenylene.
 13. A composition according to claim 12, wherein the structural element of the formula (t) is norborn-1,2-enylene of the formula (nr₃)


14. A composition according to claim 10, wherein the metathesis polymer contains recurring structural units of the formula (u)

and recurring structural elements of the formula (w) —CH═CH—R₀₂₆—  (w), in which A₁, together with the —CH—CH—group, is bicyclic C₅-C₈cycloalkenylene and R₀₂₆ is C₁-C₁₂alkylene, and, if desired, recurring structural elements of the formula (s)

in which R₀₂₂ is H, F, C₁-C₁₂alkyl, —COOH, —C(O)O—C₁-C₁₂alkyl, —C(O)—NH₂ or —C(O)—NH—C₁-C₁₂alkyl; R₀₂₃ is H, F, Cl, CN or C₁-C₁₂alkyl; R₀₂₄ is H, F, Cl, CN, OH, C₁-C₁₂alkyl, C₁-alkoxy, phenyl which is unsubstituted or substituted by OH, Cl, Br, C₁-C₄alkyl, C₁-C₄alkoxy, —COOH, C(O)OC₁-C₁₂alkyl, —C(O)—NH₂, —C(O)—NH—C₁-C₁₂alkyl, —SO₃H or —SO₃—C₁-C₁₂alkyl, —C(O)OH, —C(O)O—C₂—C₁₂hydroxyalkyl, —C(O)O—C₁-C₁₂alkyl, —C(O)—NH₂ or —C(O)—NH—C₁-C₁₂alkyl; and R₀₂₅ is H, F or C₁-C₁₂alkyl.
 15. A composition according to claim 1, wherein the polymers with a carbon backbone are homo- and copolymers of 1,3-dienes and, if desired, olefinically unsaturated monomers, of which the olefinic double bonds in the polymer backbone are reacted partly or completely with open-chain or cyclic 1,3-dienes having 4 to 12 C atoms in a Diels-Alder reaction to give cycloalkenylene radicals having 6 to 14 C atoms.
 16. A composition according to claim 15, wherein 5 to 80% of the double bonds are reacted.
 17. A composition according to claim 15, wherein the 1,3-dienes are chosen from the group consisting of 1,3-butadiene, isoprene and chloroprene.
 18. A composition according to claim 15, wherein the polymers contain recurring structural elements of the formula (t),

in which A₁ is mono- or bicyclic C₅-C₈cycloalkenylene.
 19. A composition according to claim 18, wherein the structural element of the formula (t) corresponds to norbornen -1,2-enylene of the formula (nr₃)


20. A composition according to claim 15, wherein the polymer contains recurring structural units of the formula (y)

and recurring structural elements of the formula (z) —CH₂—CH═CR₀₂₇—CH₂—  (z), in which A₁, together with the —CH—CR₀₂₇ group, is bicyclic C₅-C₈cycloalkenylene and R₀₂₇ is H, Cl or C₁-C₁₂alkyl, and, if desired, recurring structural elements of the formula (s)

in which R₀₂₂ is H, F, C₁-C₁₂alkyl, —COOH, —C(O)O—C₁-C₁₂alkyl, —C(O)—NH₂ or —C(O)—NH—C₁-C₁₂alkyl; R₀₂₃ is H, F, Cl, CN or C₁-C₁₂alkyl; R₀₂₄ is H, F, Cl, CN, OH, C₁-C₁₂alkyl, C₁-C₁₂alkoxy, phenyl which is unsubstituted or substituted by OH, Cl, Br, C₁-C₄alkyl, C₁-C₄alkoxy, —COOH, C(O)OC₁-C₁₂alkyl, —C(O)—NH₂, —C(O)—NH—C₁-C₁₂alkyl, —SO₃H or —SO₃—C₁-C₁₂alkyl, —C(O)OH, —C(O)O—C₂-C₁₂hydroxyalkyl, —C(O)O—C₁-C₁₂alkyl, —C(O)—NH₂ or —C(O)—NH—C₁-C₁₂alkyl; and R₀₂₅ is H, F or C₁-C₁₂alkyl.
 21. A composition according to claim 1, wherein the comonomeric strained cycloolefins correspond to the formula l

in which Q₁ is a radical having at least one carbon atom which, together with the —CH═CQ₂— group, forms an at least 3-membered alicyclic ring which may contain one or more heteroatoms chosen from the group consisting of silicon, phosporus, oxygen, nitrogen or sulfur; and which is unsubstituted or substituted by halogen, ═O, —CN, —NO₂, R₁R₂R₃Si—(O)_(u), —COOM, —SO₃M, —PO₃M, —COO(M₁)_(1/2), —SO₃(M₁)_(1/12), —PO₃(M₁)_(1/2), C₁-C₂₀alkyl, C₁-C₂₀hydroxyalkyl C₁-C₂₀haloalkyl, C₁-C₆cyanoalkyl, C₃-C₈cycloalkyl, C₆-C₁₆aryl, C₇-C₁₆aralkyl, C₃-C₆heterocycloalkyl, C₃-C₆heteroaryl, C₄-C₁₆heteroaralkyl or R₄—X—; or in which two adjacent C atoms are substituted by —CO—O—CO— or —CO—NR₅—CO—; or in which an alicyclic, aromatic or heteroaromatic ring which is unsubstituted or substituted by halogen, —CN, —NO₂, R₆R₇R₈Si—(O)_(u)—, —COOM, —SO₃M, —PO₃M, —COO(M₁)_(1/2), —SO₃(M₁)_(1/2), —PO₃(M₁)_(1/2), C₁-C₂₀alkyl, C₁-C₂₀haloalkyl, C₁-C₂₀hydroxyalkyl, C₁-C₆cyanoalkyl, C₃-C₈cycloalkyl, C₆-C₁₆aryl, C₇-C₁₆aralkyl, C₃-C₆heterocycloalkyl, C₃-C₁₆heteroaryl, C₄-C₁₆heteroaralkyl or R₁₃—X₁—may be fused onto adjacent carbon atoms of the alicyclic ring; X and X₁ independently of one another are —O—, —S—, —CO—, —SO—, —SO₂—, —O—C(O)—, —C(O)—O—, —C(O)—NR₅—, —NR₁₀—C(O)—, —SO₂—O— or —O—SO₂—; R₁, R₂ and R₃ independently of one another are C₁-C₁₂alkyl, C₁-C₁₂perfluoroalkyl, phenyl or benzyl; R₄ and R₁₃ independently are C₁-C₂₀alkyl, C₁-C₂₀haloalkyl, C₁-C₂₀hydroxyalkyl, C₃-C₈cycloalkyl, C₆-C₁₆aryl, C₇-C₁₆aralkyl; R₅ and R₁₀ independently of one another are hydrogen, C₁-C₁₂alkyl, phenyl or benzyl, where the alkyl groups in their turn are unsubstituted or substituted by C₁-C₁₂alkoxy or C₃-C₈cycloalkyl; R₆, R₇ and R₈ independently of one another are C₁-C₁₂alkyl, C₁-C₁₂perfluoroalkyl, phenyl or benzyl; M is an alkali metal and M₁ is an alkaline earth metal; and u is 0 or 1; where the alicyclic ring formed with Q₁, may contain further non-aromatic double bonds; Q₂ is hydrogen, C₁-C₂₀alkyl, C₁-C₂₀haloalkyl, C₁-C₁₂alkoxy, halogen, —CN, R₁₁—X₂—; R₁₁ is C₁-C₂₀alkyl, C₁-C₂₀haloalkyl, C₁-C₂₀hydroxyalkyl, C₃-C₈cycloalkyl, C₆-C₁₆aryl or C₇-C₁₆aralkyl; X₂ is —C(O)—O— or —C(O)—NR₁₂—; R₁₂ is hydrogen, C₁-C₁₂alkyl, phenyl or benzyl; where the abovementioned cycloalkyl, heterocycloalkyl, aryl, heteroaryl, aralkyl and heteroaralkyl groups are unsubstituted or substituted by C₁-C₁₂alkyl, C₁C₁₂alkoxy, —NO₂, —CN or halogen and where the heteroatoms of the abovementioned heterocycloalkyl, heteroaryl and heteroaralkyl groups are chosen from the group consisting of —O—, —S—, —NR₉— and —N═; and R₉ is hydrogen, C₁-C₁₂alkyl, phenyl or benzyl.
 22. A composition according to claim 1, which comprises comonomeric polyfunctional strained cycloolefins which are those of the formula (f1) (T)_(n)—U  (f1), in which T is the radical of a strained cycloolefin, U is a direct bond or an n-valent bridge group and n is an integer from 2 to
 8. 23. A composition according to claim 22, wherein the radicals T correspond to cycloolefin radicals of the formula (f2)

in which Q₁ is a radical having at least one carbon atom which, together with the —CH═CQ₂— group, forms an at least 3-membered alicyclic ring which may contain one or more heteroatoms chosen from the group consisting of silicon, phosporus, oxygen, nitrogen or sulfur; and which is unsubstituted or substituted by halogen, ═O, —CN, —NO₂, R₁R₂R₃Si—(O)_(u)—, —COOM, —SO₃M, —PO₃M, —COO(M₁)_(1/2), —SO₃(M₁)_(1/2), —PO₃(M₁)_(1/2), C₁-C₂₀alkyl, C₁-C₂₀hydroxyalkyl C₁-C₂₀haloalkyl, C₁C₆cyanoalkyl, C₃-C₈cycloalkyl, C₆-C₁₆aryl, C₇-C₁₆aralkyl, C₃-C₆heterocycloalkyl, C₃-C₁₆heteroaryl, C₄-C₁₆heteroaralkyl or R₄—X—; or in which two adjacent C atoms are substituted by —CO—O—CO— or —CO—NR₅—CO—; or in which an alicyclic, aromatic or heteroaromatic ring which is unsubstituted or substituted by halogen, —CN, —NO₂, R₆R₇R₈Si—(O)_(u)—, —COOM, —SO₃M, —PO₃M, —COO(M₁)_(1/2), —SO₃(M₁)_(1/2), —PO₃(M₁)_(1/2), C₁-C₂₀alkyl, C₁-C₂₀haloalkyl, C₁-C₂₀hydroxyalkyl, C₁-C₆cyanoalkyl, C₃-C₈cycloalkyl, C₆-Cl₁₆aryl, C₇-C₁₆aralkyl, C₃-C₆heterocycloalkyl, C₃-C₁₆heteroaryl, C₄-C₁₆heteroaralkyl or R₁₃—X₁— may be fused onto adjacent carbon atoms of the alicyclic ring; X and X₁ independently of one another are —O—, —S—, —CO—, —SO—, —SO₂—, —O—C(O)—, —C(O)—O—, —C(O)—NR₅—, —NR₁₀—C(O)—, —SO₂—O— or —O—SO₂—; R₁, R₂ and R₃ independently of one another are C₁-C₁₂alkyl, C₁-C₁₂perfluoroalkyl, phenyl or benzyl; R₄ and R₁₃ independently are C₁-C₂₀alkyl, C₁-C₂₀haloalkyl, C₁-C₂₀hydroxyalkyl, C₃-C₈cycloalkyl, C₆-C₁₆aryl, C₇-C₁₆aralkyl; R₅ and R₁₀ independently of one another are hydrogen, C₁-C₁₂alkyl, phenyl or benzyl, where the alkyl groups in their turn are unsubstituted or substituted by C₁-C₁₂alkoxy or C₃-C₈cycloalkyl; R₆, R₇ and R₈ independently of one another are C₁-C₁₂alkyl, C₁-C₁₂perfluoroalkyl, phenyl or benzyl; M is an alkali metal and M₁ is an alkaline earth metal; and u is 0 or 1; where the alicyclic ring formed with Q₁ may contain further non-aromatic double bonds; Q₂ is hydrogen, C₁-C₂₀alkyl, C₁-C₂₀haloalkyl, C₁-C₁₂alkoxy, halogen, —CN, R₁₁—X₂—; R₁₁ is C₁-C₂₀alkyl, C₁-C₂₀haloalkyl, C₁-C₂₀hydroxyalkyl, C₃-C₈cycloalkyl, C₆-C₁₆aryl or C₇-C₁₆aralkyl; X₂ is —C(O)—O— or —C(O)—NR₁₂—; R₁₂ is hydrogen, C₁-C₁₂alkyl, phenyl or benzyl; where the abovementioned cycloalkyl, heterocycloalkyl, aryl, heteroaryl, aralkyl and heteroaralkyl groups are unsubstituted or substituted by C₁-C₁₂alkyl, C₁ C₁₂alkoxy, —NO₂, —CN or halogen and where the heteroatoms of the abovementioned heterocycloalkyl, heteroaryl and heteroaralkyl groups are chosen from the group consisting of —O—, —S—, —NR₉— and —N═; and R₉ is hydrogen, C₁-C₁₂alkyl, phenyl or benzyl.
 24. A composition according to claim 22, wherein U is a) a divalent bridge group of the formula (f5) —X₅—R₀₂₈—X₆—  (f5),  in which X₅ and X₆ independently of one another are a direct bond, —O—, —CH₂—O—, —C(O)O—, —O(O)C—, —CH₂—O(O)C—, —C(O)—NR₀₂₉—, —R₀₂₉N—(O)C—, —NH—C(O)—NR₀₂₉—, —O—C(O)—NH—, —CH₂—O—C(O)—NH— or —NH—C(O)—O—, and R₀₂₈ is C₂-C₁₈alkylene, C₅-C₈cycloalkylene which is unsubstituted or substituted by C₁-C₄alkyl or C₁-C₄alkoxy, C₆-C₁₈arylene or C₇-C₁₉aralkylene which are unsubstituted or substituted by C₁-C₄alkyl or C₁-C₄alkoxy, or polyoxaalkylene having 2 to 12 oxaalkylene units and 2 to 6 C atoms in the alkylene, and R₀₂₉ is H or C₁-C₆alkyl; or (b) a trivalent bridge group of the formula (f6)

 in which X₅, X₆ and X₇ are —O—, —CH₂—O—, —C(O)O—, —O(O)C—, —CH₂—O(O)C—, —C(O)—NR₀₂₉—, —R₀₂₉N—(O)C—, —NH—C(O)—NR₀₂₉—, —O—C(O)—NH—, —CH₂—O—C(O)—NH— or —NH—C(O)—O—, and R₀₃₁ is a trivalent aliphatic hydrocarbon radical having 3 to 20 C atoms, a trivalent cycloaliphatic radical which has 3 to 8 C atoms and is unsubstituted or substituted by C₁-C₄alkyl or C₁-C₄alkoxy, or a trivalent aromatic radical having 6 to 18 C atoms, which is unsubstituted or substituted by C₁-C₄alkyl or C₁-C₄alkoxy, a trivalent araliphatic radical having 7 to 19 C atoms, which is unsubstituted or substituted by C₁-C₄alkyl or C₁-C₄alkoxy, or a trivalent heteroaromatic radical having 3 to 13 C atoms and 1 to 3 heteroatoms from the group consisting of —O—, —N—and —S—, which is unsubstituted or substituted by C₁-C₄alkyl or C₁-C₄alkoxy, and R₀₃₁ is H or C₁-C₆alkyl; or (c) a tetravalent bridge group of the formula (f7)

 in which X₅, X₆, X₇ and X₈ are —C(O)O—, —CH₂—O(O)C— or —C(O)—NR₀₂₉—, and R₀₃₂ is a tetravalent aliphatic hydrocarbon radical having 4 to 20 C atoms, a tetravalent cycloaliphatic radical having 4 to 8 ring C atoms, which is unsubstituted or substituted by C₁-C₄alkyl or C₁-C₄alkoxy, or a tetravalent aromatic radical having 6 to 18 C atoms, which is unsubstituted or substituted by C₁-C₄alkyl or C₁-C₄alkoxy, a tetravalent araliphatic radical having 7 to 19 C atoms, which is unsubstituted or substituted by C₁-C₄alkyl or C₁-C₄alkoxy, or a tetravalent heteroaromatic radical having 3 to 13 C atoms and 1 to three heteroatoms from the group consisting of —O—, —N— and —S—, which is unsubstituted or substituted by C₁-C₄alkyl or C₁-C₄alkoxy, and R₀₂₉ is H or C₁-C₆alkyl.
 25. A composition according to claim 1, which comprises polymers and, if desired, monomers which are built up only from carbon and hydrogen.
 26. A composition according to claim 1, which comprises the one-component catalyst in an amount of 0.001 to 20 mol %, based on the amount of the monomer.
 27. A composition according to claim 26, which comprises the one-component catalyst in an amount of 0.01 to 10 mol %, based on the amount of the monomer. 